RU2171815C2 - Composition for preparing metathesis polymerizates - Google Patents

Abstract

FIELD: chemistry of polymers. SUBSTANCE: described is new composition for preparing metathesis polymerizates from (a) at least one compound of formula: (A)_n-B -X₅-R₂₀-X₆(I) wherein A is radical of hindered cycloolefin, B is direct bond of bridge group X₅ and X₆ wherein R₂₀ is direct bon, and C₂-C₁₈ is C₁-C₄ alkylene, unsubstituted or substituted by C₇-C₁₉ alkyl; or

Description

 The invention relates to compounds with at least two hindered cycloolefins bonded directly or via a bridging group; formulations having these compounds and one one-component catalyst for carrying out the polymerization process when heated and / or irradiated; a polymerization method, crosslinked polymers obtained from these compounds and, if necessary, from other olefins and / or cycloolefins suitable for polymerization; carriers coated with a layer of these crosslinked polymers and polymerization methods.

W093 / 13171 describes one and two component catalysts resistant to atmospheric and water effects based on molybdenum and tungsten compounds, as well as ruthenium and osmium containing carbonyl groups, with at least one poly linked group for the thermal and photoactivation polymerization of hindered cycloolefins, in particular norbornene and norbornene derivatives. Other polycyclic, especially non-condensed polycyclic cycloolefins are not mentioned. The single component ruthenium compound catalysts used, i.e. [(C ₆ H ₆ ) Ru (CH ₃ CN) ₂ Cl] ⁺ PF ₆ ^- and [Ru (cumene) Cl ₂ ] ₂ can be activated by ultraviolet irradiation, however, the storage stability of compositions containing norbornene is extremely unsatisfactory . These catalysts cannot sufficiently replace the known two-component catalysts.

Demonceau et al. [Demonceau, A., Noels, AF, Saive, E., Hubert, AJ, J. Mol. Catal. (76: 123-132 (1992)] describe [(C ₆ H ₅ ) ₃ ] ₃ PRuCl ₂ , (p-cumene) RuCl ₂ P (C ₆ H ₁₁ ) ₃ and [(C ₆ H ₅ ) ₃ ] ₃ PRuHCl as thermal catalysts for the polymerization process with ring opening of norbornene, condensed polycycloolefin. These catalysts could not be used in industrial production because of their limited activity. Therefore, it is proposed to increase activity by adding a diazoester. It is also mentioned that only (p-cumene ) RuCl ₂ P (C ₆ H _{11) 3} capable of polymerizing norbornene relatively rapidly at a temperature of 60 ^o C. as rugogo monomer named cyclooctene. Other cycloolefins suitable for such polymerization are not called.

 Petasis und Fu [Petasis, N. A., Fu, D., J. Am. Chem. Soc. 115: 7208-7214 (1993)] describe a thermal polymerization process with opening the norbornene ring using biscyclopentadienyl bis (trimethylsilyl) methyl titanium (IV) as a thermally active catalyst. Other cycloolefins suitable for carrying out such a polymerization process are not called.

и соединения формулы

которые получаются при использовании катализаторных систем для проведения процесса термической полимеризации, состоящих из катализатора и активатора. Недостатком этих систем является необходимость разделения катализатора и активатора, так что нельзя приготовить устойчивые при хранении составы, способные полимеризоваться. Катализатор и активатор можно соединить только непосредственно перед полимеризацией, причем получаются высокореактивные и быстро густеющие при выделении тепла составы. Поэтому получение тел формованием ограничивается известными способами, например в результате RIM-процесса. Получаемые сетчатые полимеризаты имеют высокие температуры размягчения. Покрытые слоем материалы не упоминаются.EP 287762 describes crosslinked copolymers consisting of a mixture of 1,2-bisnorbornenyl-ethane of the formula

and compounds of the formula

which are obtained using catalyst systems for carrying out the process of thermal polymerization, consisting of a catalyst and an activator. The disadvantage of these systems is the need for separation of the catalyst and the activator, so that it is impossible to prepare stable during storage compositions capable of polymerization. The catalyst and activator can be combined only immediately prior to polymerization, and highly reactive and rapidly thickening compositions are formed upon heat evolution. Therefore, obtaining bodies by molding is limited by known methods, for example, as a result of the RIM process. The resulting crosslinked polymerizates have high softening temperatures. Coated materials are not mentioned.

 It was found that the compositions of hindered cycloolefin compounds bonded directly or via a bridging group and a one-component catalyst are storage stable and exhibit exceptional processability, depending on the choice of catalyst, even in the presence of oxygen and humidity. These compositions can be processed without any special precautions to obtain cross-linked polymerizates using various molding methods. Polymerizates have high densities of formation of the polymer network and exceptional mechanical and electrical properties, as well as surface properties, for example low values of ∈ and tan δ values, as well as very low water absorption. The monomers used are excellent film formers, and polymer films have exceptional properties. In addition, it was found that thanks to these compositions receive coatings in the form of cross-linked polymers, which have extremely high adhesion even on smooth metal surfaces. Stability during storage allows you to use varnishes, photoresists, glue as coatings and get by molding any type of body. In addition, it is possible to obtain polymers in the form of rubber or thermoplastic polymers, which can then form a polymer network.

The subject of the invention are compounds of formula I
(A) _n -B, (I)
where A is the radical of a cycloolefin hindered, B stands for a direct bond or an n-valent bridging group, and n is an integer from 2 to 8, except 1,2-bisnorbornenyl ethane and norbornene carboxylic acid methyl ester.

 With respect to cyclic olefins, one can speak of monocyclic or polycyclic fused ring systems and / or closed bridged ring systems, for example with two to four rings, unsubstituted or substituted and having heteroatoms, such as O, S, N or Si in one or more rings and / or fused alicyclic, aromatic or heteroaromatic rings, such as o-cyclopentylene, o-phenylene, o-naphthylene, o-pyridinyl or o-pyrimidinyl. Individual cyclic rings may contain from 3 to 16, preferably from 3 to 12, and most preferably from 3 to 8 ring elements. Cyclic olefins may have other non-aromatic double bonds, depending on the size of the ring, preferably from 2 to 4 such additional double bonds. Regarding ring substituents, we are talking about those which are inert, i.e. about those that do not violate the chemical stability of single-component catalysts.

 The fused alicyclic rings preferably contain from 3 to 8, most preferably from 4 to 7, and most preferably 5 or 6 carbon ring atoms.

где Q₁ является радикалом по меньшей мере с одним атомом углерода, образующим вместе с группой -CH=CQ₂ одно, по меньшей мере трехчленное алициклическое кольцо, содержащее при известных условиях один гетероатом или несколько гетероатомов, выбранных из группы, состоящей из силиция, фосфора, кислорода, азота и серы, и незамещенным или замещенным галогеном, =O, -CN, -NO₂, R₁R₂R₃Si-(O)_u, -COOM, -SO₃M, -PO₃M, -COO(M₁)_1/2, -SO₃(M₁)_1/2, -PO₃(M₁)_1/2, C₁-C₂₀-алкилом, C₁-C₂₀-гидроксиалкилом, C₁-C₂₀-галогеналкилом,
C₁-C₆-цианоалкилом, C₃-C₈-циклоалкилом, C₆-C₁₆-арилом, C₇-C₁₆-аралкилом,
C₃-C₆-гетероциклоалкилом, C₃-C₁₆-гетероарилом, C₄-C₁₆-гетероаралкилом или R₄-X-; или у которого два соседних углеродных атома заменены -CO-O-CO- или -CO-NR₅-CO-, или у которого при известных условиях у соседних атомов углерода алициклического кольца сконденсированы одно ароматическое или гетероароматическое кольцо и/или другие алициклические кольца, незамещенные или замещенные галогеном, -CN, -NO₂, R₆R₇R₈Si-(O)_u, -COOM, -SO₃M, PO₃M, -COO(M₁)_1/2, -SO₃(M₁)_1/2, -PO₃(M₁)_1/2, C₁-C₂₀-алкилом, C₁-C₂₀-галогеналкилом, C₁-C₂₀-гидроксиалкилом, C₁-C₆-цианоалкилом, C₃-C₈-циклоалкилом, C₆-C₁₆-арилом, C₇-C₁₆-аралкилом, C₃-C₆-гетероциклоалкилом, C₃-C₁₆-гетероарилом, C₄-C₁₆-гетероаралкилом или R₁₃-X₁-;
X и X₁ независимо друг от друга стоят вместо -O-, -S-, -CO-, -SO-, -SO₂, -O-C(O)-, -C(O)-O, -C(O)-NR₅-, -NR₁₀-C(O)-, - SO₂-O- или -O-SO₂-;
R₁, R₂ и R₃ независимо друг от друга обозначают C₁-C₁₂-алкил, C₁-C₁₂-перфторалкил, фенил или бензил;
R₄ и R₁₃ независимо друг от друга обозначают C₁-C₂₀-алкил, C₁-C₂₀-галогеналкил, C₁-C₂₀-гидроксиалкил, C₃-C₈-циклоалкил, C₆-C₁₆-арил, C₇-C₁₆-аралкил;
R₅ и R₁₀ независимо друг от друга обозначают водород, C₁-C₁₂- алкил, фенил или бензил, причем алкиловые группы являются, в свою очередь, незамещенными или замещенными C₁-C₁₂-алкоксилом или C₃-C₈-циклоалкилом;
R₆, R₇ и R₈ независимо друг от друга обозначают C₁-C₁₂-алкил, C₁-C₁₂-перфторалкил, фенил или бензил;
М стоит вместо щелочного металла, а М₁ - вместо щелочноземельного металла; и
u стоит вместо 0 или 1;
причем образованное с помощью Q₁ алициклическое кольцо содержит при известных условиях другие, неароматические двойные связи;
Q₂ обозначает водород, C₁-C₂₀-алкил, C₁-C₂₀-галогеналкил, C₁-C₁₂-алкоксил, галоген, -CN или R₁₁-X₂-;
R₁₁ обозначает C₁C₂₀-алкил, C₁-C₂₀-галогеналкил, C₁-C₂₀-гидроксиалкил, C₃-C₈-циклоалкил, C₆-C₁₆-арил или C₇-C₁₆-аралкил;
X₂ обозначает -C(O)-O- или -C(O)-NR₁₂-;
R₁₂ представляет собой водород, C₁-C₁₂-алкил, фенил или бензил; причем вышеназванные группы циклоалкила, гетероциклоалкила, арила, гетероарила, аралкила и гетероаралкила являются незамещенными или замещенными C₁-C₁₂-алкилом, C₁-C₁₂-алкоксилом, -NO₂, -CN или галогеном, и причем гетероатомы вышеназванных групп гетероциклоалкила, гетероарила и гетероаралкила выбраны из группы -O-, -S- -NR₉- и -N=; и
R₉ представляет водород, C₁-C₁₂-алкил, фенил или бензил.In one preferred embodiment, the radicals A in formula I correspond to the radicals of cycloolefins of formula II

where Q ₁ is a radical with at least one carbon atom, forming together with the group -CH = CQ ₂ one at least a three-membered alicyclic ring containing, under certain conditions, one heteroatom or several heteroatoms selected from the group consisting of silicon and phosphorus , oxygen, nitrogen and sulfur, and unsubstituted or substituted by halogen, = O, —CN, —NO ₂ , R ₁ R ₂ R ₃ Si— (O) _u , —COOM, —SO ₃ M, —PO ₃ M, - COO (M ₁ ) _1/2 , -SO ₃ (M ₁ ) _1/2 , -PO ₃ (M ₁ ) _1/2 , C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ hydroxyalkyl, C ₁ - C ₂₀ halogenated,
C ₁ -C ₆ cyanoalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₆ aryl, C ₇ -C ₁₆ aralkyl,
C ₃ -C ₆ heterocycloalkyl, C ₃ -C ₁₆ heteroaryl, C ₄ -C ₁₆ heteroaralkyl or R ₄ -X-; or in which two adjacent carbon atoms are replaced by -CO-O-CO- or -CO-NR ₅ -CO-, or in which, under certain conditions, one aromatic or heteroaromatic ring and / or other alicyclic rings are condensed on adjacent carbon atoms of the alicyclic ring, unsubstituted or substituted by halogen, —CN, —NO ₂ , R ₆ R ₇ R ₈ Si— (O) _u , —COOM, —SO ₃ M, PO ₃ M, —COO (M ₁ ) _1/2 , —SO ₃ (M ₁ ) _1/2 , -PO ₃ (M ₁ ) _1/2 , C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₂₀ hydroxyalkyl, C ₁ -C ₆ cyanoalkyl , C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₆ aryl, C ₇ -C ₁₆ aralkyl, C ₃ -C ₆ heterocycloalkyl, C ₃ -C ₁₆ heteroaryl, C ₄ -C ₁₆ heteroaralkyl or R ₁₃ -X ₁ -;
X and X _{1 are} independently of each other instead of -O-, -S-, -CO-, -SO-, -SO ₂ , -OC (O) -, -C (O) -O, -C (O) —NR ₅ -, —NR ₁₀ —C (O) -, —SO ₂ —O— or —O — SO ₂ -;
R ₁ , R ₂ and R _{3 are} independently C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ perfluoroalkyl, phenyl or benzyl;
R ₄ and R _{13 are} independently C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₂₀ hydroxyalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₆ aryl, C ₇ -C ₁₆ aralkyl;
R ₅ and R _{10 are} independently hydrogen, C ₁ -C ₁₂ alkyl, phenyl or benzyl, the alkyl groups being, in turn, unsubstituted or substituted with C ₁ -C ₁₂ alkoxy or C ₃ -C ₈ - cycloalkyl;
R ₆ , R ₇ and R _{8 are} independently C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ perfluoroalkyl, phenyl or benzyl;
M stands for alkali metal, and M ₁ stands for alkaline earth metal; and
u stands for 0 or 1;
moreover, the alicyclic ring formed with Q ₁ contains, under certain conditions, other, non-aromatic double bonds;
Q ₂ is hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₂ alkoxy, halogen, —CN or R ₁₁ —X ₂ -;
R ₁₁ is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₂₀ hydroxyalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₆ aryl or C ₇ -C ₁₆ aralkyl;
X ₂ is —C (O) —O— or —C (O) —NR ₁₂ -;
R ₁₂ represents hydrogen, C ₁ -C ₁₂ alkyl, phenyl or benzyl; moreover, the above groups of cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroalkyl are unsubstituted or substituted by C ₁ -C ₁₂ -alkyl, C ₁ -C ₁₂ -alkoxyl, -NO ₂ , -CN or halogen, and wherein the heteroatoms of the above heteroalkyl groups heteroaryl and heteroalkyl are selected from the group —O—, —S— —NR ₉ - and —N =; and
R ₉ represents hydrogen, C ₁ -C ₁₂ alkyl, phenyl or benzyl.

 The position of the double bond in the ring of formula II to obtain a free bond depends largely on the size of the ring and the method for producing compounds of formula I.

 If the compounds of formula II have an asymmetry center, this leads to the fact that the compounds can arise in the form of optical isomers. Some compounds of formula II may appear in the form of tautomers (for example, keto-enol tautomerism). If there is an aliphatic double bond C = C, then geometric isomerism (E-form or Z-form) can also occur. In addition, configurations outside and inside the ring are also possible. Thus, Formula II covers all possible stereoisomers presented in the form of enantiomers, tautomers, geometric isomers of ethylene compounds, E / Z isomers, or mixtures thereof.

 In the definitions of substituents, straight or branched chain alkyl, alkenyl or alkynyl groups may be represented. The same applies to each part of the alkyl groups of alkoxyl, alkylthio, alkoxycarbonyl and other groups containing alkyl. These alkyl groups preferably contain from 1 to 12, most preferably from 1 to 8, and most preferably from 1 to 4 carbon atoms. These alkenyl and alkynyl groups preferably contain from 2 to 12, most preferably from 2 to 8, and most preferably from 2 to 4 carbon atoms.

 Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl, secondary butyl, tertiary butyl, as well as various isomeric radicals of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and aikosil.

 Hydroxyalkyl includes, for example, hydroxymethyl, hydroxyethyl, 1-hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl, 1-hydroxy-isobutyl, 1-hydroxy-secondary-butyl, 1- hydroxy-tertiary.-butyl, as well as various isomeric radicals of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and ekey.

 Haloalkyl includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, as well as halogenated, in particular fluorinated or chlorinated alkanes, such as, for example, isopropyl, n-propyl, n-butyl, iso-butyl, secondary-butyl, tertiary-butyl, and various isomeric radicals of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl , dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosil.

 Alkenyl includes, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec -2-enyl, isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl.

With respect to cycloalkyl, it is preferably a C ₅ -C ₈ cycloalkyl, in particular a C ₅ or C ₆ cycloalkyl. Some examples are cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

 Cyanoalkyl includes, for example, cyanomethyl (methyl nitrile), cyanoethyl (ethyl nitrile), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl, 1-cyano-isobutyl, 1-cyano-secondary . - butyl, 1-cyano-tertiary.-butyl, as well as various isomeric radicals of cyanopentyl and cyanohexyl.

 Aralkyl preferably contains from 7 to 12 carbon atoms and most preferably from 7 to 10. We can speak, for example, of benzyl, phenethyl, 3-phenylpropyl, α-methylbenzyl, phenbutyl or α, α-dimethylbenzyl.

 Aryl preferably contains from 6 to 10 carbon atoms. You can talk, for example, about phenyl, pentalin, indene, naphthalene, azulin or anthracene.

 Heteroaryl preferably contains from 4 to 5 carbon atoms and one or two heteroatoms from the group O, S and N. One can speak, for example, of pyrrole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, purine or quinoline.

 Heterocycloalkyl preferably contains 4 or 5 carbon atoms and one or two heteroatoms from the group O, S, and N. For example, oxirane, azirine, 1,2-oxathiolane, pyrazoline, pyrrolidine, piperidine, piperazine, morpholine, tetrahydrofuran or tetrahydrothiophene .

 An alkoxyl is, for example, methoxyl, ethoxyl, propyloxyl, i-propyloxy, n-butyloxyl, i-butyloxyl, and secondary. butyloxy or t-butyloxy.

 Under the alkaline metals in the framework of the proposed invention refers to lithium, sodium, potassium, rubidium and cesium, in particular lithium, sodium and potassium.

 Under the alkaline earth metals in the framework of the proposed invention refers to beryllium, magnesium, calcium, strontium and barium, in particular magnesium and calcium.

 In the above definitions, halogen means fluoro, chloro, bromo and iodo, preferably fluoro, chloro and bromo.

In the radicals of formula II, Q ₂ is preferably hydrogen.

In addition, compounds with radicals of the formula II are preferred, wherein the alicyclic ring formed with Q ₁ together with the group —CH═CQ ₂ has from 3 to 16, preferably from 3 to 12, and most preferably from 3 to 8 ring atoms, and moreover, it may be a monocyclic, bicyclic, tricyclic or tetracyclic fused ring system.

With particular advantage, the claimed method can be implemented using such compounds having radicals of formula II, where Q ₁ is a radical with at least one carbon atom, which together with the group -CH = CQ ₂ forms an alicyclic ring having from 3 to 20 elements and under certain conditions, one or more heteroatoms selected from the group of silicon, oxygen, nitrogen and sulfur; which is unsubstituted or substituted by halogen, = O, —CN, —NO ₂ , R ₁ R ₂ R ₃ Si— (O) _u , COOM, —SO ₃ M, —PO ₃ M, —COO (M ₁ ) _{1 / 2} , -SO ₃ (M ₁ ) _1/2 , -PO ₃ (M ₁ ) _1/2 , C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ halogenated, C ₁ -C ₁₂ hydroxyalkyl, C ₁ C ₄ cyanoalkyl, C ₃ -C ₆ cycloalkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₂ aralkyl, C ₃ -C ₆ heterocycloalkyl, C ₃ -C ₁₂ heteroaryl, C ₄ -C ₁₂ -heteroaralkyl or R ₄ -X-, or in which two adjacent carbon atoms in this radical Q ₁ are substituted by -CO-O-CO- or -CO-NR ₅ -CO-, or in which, under certain conditions, adjacent carbon atoms aromatic or heteroaromatic tso and / or other alicyclic ring unsubstituted or substituted by halogen, -CN, -NO _2, R ₆ R ₇ R ₈ Si-, -COOM, SO ₃ M, -RO ₃ M, -COO (M _{1) 1/2} , -SO ₃ (M ₁ ) _1/2 , -PO ₃ (M ₁ ) _1/2 , C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₁₂ hydroxyalkyl, C ₁ - C ₄ -cyanoalkyl, C ₃ -C ₆ cycloalkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₂ aralkyl, C ₃ -C ₆ heterocycloalkyl, C ₃ -C ₁₂ heteroaryl, C ₄ -C ₁₂ Heteroaralkyl or R ₁₃ —X ₁ -;
X and X _{1 are} independently of each other instead of -O-, -S-, -CO-, -SO-, -SO ₂ -, -OC (O) -, -C (O) -O-, -C ( O) —NR ₅ , —NR ₁₀ —C (O) -, —SO ₂ —O— or —O — SO ₂ -, and
R ₁ , R ₂ and R _{3 are} independently C ₁ -C ₆ alkyl, C ₁ -C ₆ perfluoroalkyl, phenyl or benzyl;
M stands for alkali metal, and M ₁ stands for alkaline earth metal;
R ₄ and R _{13 are} independently C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₁₂ hydroxyalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₂ aralkyl;
R ₅ and R _{10 are} independently hydrogen, C ₁ -C ₆ alkyl, phenyl or benzyl,
moreover, the alkyl groups are, in turn, unsubstituted or substituted by C ₁ -C ₆ alkoxy or C ₃ -C ₆ cycloalkyl;
R ₆ , R ₇ and R ₈ independently represent C ₁ -C ₆ alkyl, C ₁ -C ₆ perfluoroalkyl, phenyl or benzyl;
u stands for 0 or 1;
wherein the alicyclic ring formed with Q ₁ contains, under certain conditions, other non-aromatic double bonds;
Q ₂ is hydrogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₆ alkoxy, halogen, —CN or R ₁₁ —X ₂ -;
R ₁₁ is C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₁₂ hydroxyalkyl, C ₃ -C ₆ cycloalkyl, C ₆ -C ₁₂ aryl or C ₇ -C ₁₂ aralkyl ; X ₂ is —C (O) —O— or —C (O) —NR ₁₂ and
R ₁₂ is hydrogen, C ₁ -C ₆ alkyl, phenyl or benzyl;
and wherein the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroalkyl groups are unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, -NO ₂ , -CN or halogen, and wherein the hetero atoms of the heterocycloalkyl, heteroaryl groups and heteroaralkyl are selected from the group —O—, —S—, —NR ₉ and —N =;
R ₉ is hydrogen, C ₁ -C ₆ alkyl, phenyl or benzyl.

Of this group, those compounds with a radical of formula II are preferred where
Q ₁ is a radical with at least one carbon atom, which together with the group -CH = CQ ₂ forms a 3-10 membered alicyclic ring containing, under certain conditions, a heteroatom from the group of silicon, oxygen, nitrogen and sulfur, and which is unsubstituted or substituted halogen, —CN, —NO ₂ , R ₁ R ₂ R ₃ Si—, —COOM, —SO ₃ M, —PO ₃ M, —COO (M ₁ ) _1/2 , —SO ₃ (M ₁ ) _{1 / 2} , -PO ₃ (M ₁ ) _1/2 ,
C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ hydroxyalkyl, C ₁ -C ₄ cyanoalkyl, C ₃ -C ₆ cycloalkyl, phenyl, benzyl or R ₄ -X-; or in which an aromatic or heteroaromatic ring, unsubstituted or substituted by halogen, —CN, —NO ₂ , R ₆ R ₇ R ₈ Si—, —COOM, —SO ₃ M, —PO ₃ M -COO (M ₁ ) _1/2 , -SO ₃ (M ₁ ) _1/2 , -PO ₃ (M ₁ ) _1/2 , C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ hydroxyalkyl, C ₁ -C ₄ cyanoalkyl, C ₃ -C ₆ cycloalkyl, phenyl, benzyl or R ₁₃ -X ₁ -;
R ₁ , R ₂ and R _{3 are} independently C ₁ -C ₄ alkyl, C ₁ -C ₄ perfluoroalkyl, phenyl or benzyl;
M stands for alkali metal, and M ₁ stands for alkaline earth metal;
R ₄ and R _{13 are} independently C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ hydroxyalkyl or C ₃ -C ₆ cycloalkyl;
X and X _{1 are} independently of each other instead of —O—, —S—, —CO—, —SO— or —SO ₂ -;
R ₆ , R ₇ and R ₈ independently of each other are C ₁ -C ₄ alkyl, C ₁ -C ₄ perfluoroalkyl, phenyl or benzyl; and
Q ₂ is hydrogen.

 For a cycloolefin radical of formula II, unsubstituted or substituted cyclopropenyl, cyclobutenyl, cyclopentenyl, cycloheptenyl, cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl or norbornenyl or norbornenyl derivatives, such as, for example, 7-oxo-2,2-2,2 as well as the corresponding derivatives of benzoyl.

C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy are the most preferred substituents.

где X₃ обозначает -CHR₁₆-, кислород или серу;
R₁₄ и R₁₅ независимо друг от друга обозначают водород, -CN, трифторметил, (CH₃)₃Si-O-, (CH₃)₃Si-O- или -CООR₁₇; и
R₁₆ и R₁₇ независимо друг от друга обозначают водород, C₁-C₁₂-алкил, фенил или бензил;
или формуле IV

где X₄ обозначает -CHR₁₉-, кислород или серу;
R₁₉ обозначает водород, C₁-C₁₂-алкил, фенил или бензил; а
R₁₈ обозначает водород, C₁-C₆-алкил или галоген.Suitable radicals of formula II are, in particular, norbornenyl and derivatives of norbornenyl. Among the norbornenyl derivatives, those which correspond to either formula III are most preferred.

where X ₃ is —CHR ₁₆ -, oxygen or sulfur;
R ₁₄ and R _{15 are} independently hydrogen, —CN, trifluoromethyl, (CH ₃ ) ₃ Si — O—, (CH ₃ ) ₃ Si — O— or —COOR ₁₇ ; and
R ₁₆ and R _{17 are} independently hydrogen, C ₁ -C ₁₂ alkyl, phenyl or benzyl;
or formula IV

where X ₄ is —CHR ₁₉ -, oxygen or sulfur;
R ₁₉ is hydrogen, C ₁ -C ₁₂ alkyl, phenyl or benzyl; a
R ₁₈ is hydrogen, C ₁ -C ₆ alkyl or halogen.

В формуле I n стоит предпочтительно вместо целого числа от 2 до 6, наиболее предпочтительно от 2 до 4, а лучше всего вместо 2 или 3.With respect to the cycloolefin radical of the formula II, it is preferably a norbornenyl of the formula

In the formula, I n is preferably instead of an integer from 2 to 6, most preferably from 2 to 4, and most preferably instead of 2 or 3.

 In formula I, B denotes preferably an n-valent bridging group.

As divalent bridge groups are, for example, such groups of formula V
-X ₅ -R _2O -X ₆ -, (V)
where X ₅ and X ₆ independently of each other denote a direct bond, -O-, CH ₂ O-, -C (O) O-, -O (O) C-, -CH ₂ O (O) C-, - C (O) -NR ₂₁ , -R ₂₁ N- (O) C -, - NH-C (O) -NR ₂₁ -, -OC (O) -NH-, -CH ₂ OC (O) -NH- or —NH — C (O) —O—; and
R ₂₀ is C ₂ -C ₁₈ alkylene unsubstituted or substituted with C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxyl C ₅ -C ₈ cycloalkylene unsubstituted or substituted with C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxyl C ₆ -C ₈ arylene or C ₇ -C ₁₉ aralkylene, or polyoxaalkylene with oxaalkylene units in an amount of from 2 to 12 and with carbon atoms in alkylene in an amount of from 2 to 6, and
R ₂₁ is hydrogen or C ₁ -C ₆ alkyl.

R ₂₀ , as alkylene, contains from 2 to 12, most preferably from 2 to 8 carbon atoms. Alkylene may have a straight or branched chain. The most preferred cycloalkylene is cyclopentylene, and preferably cyclohexylene. Some examples of arylene are phenylene, naphthylene, biphenylene, biphenylene ether, and anthracene. An example of aralkylene is benzylene. Polyoxaalkylene preferably contains from 2 to 6, most preferably from 2 to 4 units, and preferably 2 or 3 carbon atoms in alkylene.

In one of the preferred embodiments in the formula V
a) X ₅ and X ₆ are instead of a direct bond, and R ₂₀ is instead of C ₂ -C ₁₈ alkylene, preferably instead of C ₂ -C ₁₂ alkylene, or
b) X ₅ and X ₆ are instead of -O-, -CH ₂ -O-, -C (O) O-, -O (O) C-, -CH ₂ -O (O) C-, -C ( O) —NR ₂₁ -, —OC (O) —NH— or —CH ₂ —OC (O) —NH—, and R _{20 is} substituted for C ₂ -C ₁₂ alkylene, unsubstituted or substituted with C ₁ -C ₄ - alkyl or C ₁ -C ₄ alkoxy of phenylene, naphthylene or benzylene or -R ₂₂ - (OR ₂₂ -) _x , where x is an integer from 2 to 4, and R ₂₂ is C ₂ -C ₄ -alkylene.

 Some examples of compounds of formula I having a divalent bridging group are (0) - (17), presented at the end of the description.

Compounds of formula I containing a bridging group of formula V, which is a pure hydrocarbon bridge, are obtained, for example, by the reaction of a cyclic diene with an aliphatic diene having a straight or branched chain (Diels-Alder reaction) (see also EP 287762), moreover, mixtures of substances are often formed, which are then either used immediately or first separated by conventional means. Compounds of formula I having a bridging group of formula V, wherein X ₅ and X ₆ are not a direct bond, are prepared from the corresponding halides or dihalides, alcohols or diols, amines or diamines, carboxylic acids or dicarboxylic acids or isocyanates or diisocyanates in a known manner using ether, ester or amidation reactions.

где X₅, X₆ и X₇ обозначают -O-, -CH₂O-, -C(O)O-, -O(O)С-, -CH₂-O(O)C-, -C(O)-NR₂₁-, -R₂₁N-(O)C-, -NH-C(O)-NR₂₁, -O-C(O)-NH-, -CH₂-O-C(O)-NH- или -NH-C(O)-O-, и
R₂₃ обозначает трехвалентный алифатический углеводородный радикал с атомами углерода в количестве от 3 до 20, предпочтительно от 3 до 12, трехвалентный незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом циклоалифатический радикал с углеродными атомами кольца в количестве от 3 до 8, предпочтительно 5 или 6, или трехвалентный незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом ароматический радикал с углеродными атомами в количестве от 6 до 18, предпочтительно от 6 до 12, незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом трехвалентный аралифатический радикал с углеродными атомами в количестве от 7 до 19, предпочтительно от 7 до 12, или незамещенный или замещенный C₁-С₄-алкилом или C₁-C₄-алкоксилом трехвалентный гетероароматический остаток с углеродными атомами в количестве от 3 до 13 и гетероатомами в количестве от 1 до 3 из группы -O-, -N- и -S-, а
R₂₁ является водородом или C₁-C₆-алкилом.As trivalent bridge groups are, for example, such groups of formula VI,

where X ₅ , X _6, and X ₇ are —O—, —CH ₂ O—, —C (O) O—, —O (O) C—, —CH ₂ —O (O) C—, —C ( O) -NR ₂₁ -, -R ₂₁ N- (O) C-, -NH-C (O) -NR ₂₁ , -OC (O) -NH-, -CH ₂ -OC (O) -NH- or -NH-C (O) -O-, and
R ₂₃ denotes a trivalent aliphatic hydrocarbon radical with carbon atoms in an amount of from 3 to 20, preferably from 3 to 12, a trivalent unsubstituted or substituted C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxyl cycloaliphatic radical with carbon ring atoms in an amount from 3 to 8, preferably 5 or 6, or a trivalent unsubstituted or substituted by C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxyl aromatic radical with carbon atoms in an amount of from 6 to 18, preferably from 6 to 12, unsubstituted or substituted with C ₁ -C ₄ alkyl or C ₁ -C ₄ alko xyl trivalent araliphatic radical with carbon atoms in an amount of from 7 to 19, preferably from 7 to 12, or unsubstituted or substituted by C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxyl trivalent heteroaromatic residue with carbon atoms in an amount of from 3 to 13 and heteroatoms in an amount of from 1 to 3 from the group —O—, —N— and —S—, and
R ₂₁ is hydrogen or C ₁ -C ₆ alkyl.

In one preferred embodiment, X ₅ , X ₆ and X ₇ are —O—, —CH ₂ —O—, —C (O) O—, —O (O) C—, —CH ₂ —O (O ) C-, -C (O) -NR ₂₁ -, -OC (O) -NH- or -CH ₂ -OC (O) -NH.

Preferred R ₂₃ radicals are formed, for example, from triols, such as glycerol, trimethylol propane, butanetriol, pentantriol, hexantriol, trihydroxycyclohexane, trihydroxybenzene and cyanuric acid; triamines like diethylene triamine; tricarboxylic acids, such as cyclohexanetricarboxylic acid or trimellitic acid; and triisocyanates, such as benzene triisocyanate or cyanurotriisocyanate.

 Some examples of compounds of formula I having a trivalent bridging group are (18) - (22), presented at the end of the description.

где X₅, X₆, X₇ и X₈ обозначают -C(O)O-, -CH₂-O(O)C- или -C(O)-NR₂₁, а R₂₄ представляет четырехвалентный алифатический углеводородный радикал с углеродными атомами в количестве от 4 до 20, предпочтительно от 4 до 12, четырехвалентный незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом циклоалифатический радикал с углеродными атомами кольца в количестве от 4 до 8, предпочтительно 5 или 6, или четырехвалентный незамещенный или замещенный C₁-С₄-алкилом или C₁-C₄-алкоксилом ароматический радикал с атомами углерода в количестве от 6 до 18, предпочтительно от 6 до 12, четырехвалентный незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом аралифатический радикал с атомами углерода в количестве от 7 до 19, предпочтительно от 7 до 12, или четырехвалентный незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом гетероароматический радикал с углеродными атомами в количестве от 3 до 13 и гетероатомами в количестве от 1 до 3 из группы -O-, -N- и- S-, а R₂₁ является водородом или C₁-C₆-алкилом.As tetravalent bridge groups are, for example, such groups of formula VII,

where X ₅ , X ₆ , X ₇ and X ₈ are —C (O) O—, —CH ₂ —O (O) C— or —C (O) —NR ₂₁ , and R ₂₄ is a tetravalent aliphatic hydrocarbon radical with carbon atoms in an amount of from 4 to 20, preferably from 4 to 12, a tetravalent unsubstituted or substituted by a C ₁ -C ₄ -alkyl or a C ₁ -C ₄ -alkoxyl cycloaliphatic radical with carbon atoms of the ring in an amount of from 4 to 8, preferably 5 or 6, or a tetravalent substituted or unsubstituted c ₁ -C ₄ alkyl or c ₁ -C ₄ alkoxy radical having aromatic carbon atoms in an amount of from 6 to 18, preferably 6 to 12, a substituted or unsubstituted tetravalent C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy araliphatic radical having carbon atoms in an amount of from 7 to 19, preferably from 7 to 12, or a tetravalent substituted or unsubstituted C ₁ - C ₄ -alkyl or C ₁ -C ₄ -alkoxyl heteroaromatic radical with carbon atoms in an amount of from 3 to 13 and heteroatoms in an amount of from 1 to 3 from the group -O-, -N- and S, and R ₂₁ is hydrogen or C ₁ -C ₆ alkyl.

Some examples of tetrafunctional compounds from which R ₂₄ can form are pentaerythritol, pyromellitic acid and 3,4,3 ', 4'-biphenyltetracarboxylic acid.

 As the preparation methods, the same methods can be used as for the preparation of the above compounds with a divalent or trivalent radical.

 Some examples of compounds of formula I having a tetravalent bridging group are (23) and (24), presented at the end of the description.

 As an example of higher compounds than tetravalent compounds from which bridging groups can be formed, mention could be made of polyols, such as dipentaerythritol or hexahydroxyhexane, which can be converted using the corresponding cycloolefin monobasic carboxylic acids.

 In one of the most preferred embodiments of the invention, the compounds of formula I contain only carbon and hydrogen atoms, because polymers in this regard are very environmentally valuable materials since they can be recycled using simple pyrolysis methods.

 The compounds of formula I are suitable as "crosslinking" substances during the polymerization process under the influence of heat and light rays of those compounds that are not saturated with olefins. The compounds of formula I are extremely suitable alone or in combination with other polymerizable monomers for the preparation of cross-linked polymers using thermal or photochemical single-component catalysts.

в сочетании с каталитическим количеством по меньшей мере одного термостабильного соединения молибдена (VI) или вольфрама (VI), которое имеет по меньшей мере две метиловые группы или две однозамещенные метиловые группы, связанные с металлом, причем заместитель не содержит водородный атом в положении

.The next subject of the invention is a composition of
(a) at least one compound of formula I
(A) _n -B, (I)
where A denotes a radical of a cycloolefin hindered, B stands for a direct bond or an n-valent bridging group, and n is an integer from 2 to 8, and
(b) a catalytic amount of at least one capable of being activated by heat and light rays of a one-component catalyst for carrying out the polymerization process, in addition to the (norbornene methyl) ester of norbornene carboxylic acid of the formula

in combination with a catalytic amount of at least one thermostable compound of molybdenum (VI) or tungsten (VI), which has at least two methyl groups or two monosubstituted methyl groups associated with the metal, the substituent not containing a hydrogen atom in position

.

 A, B and n have the above meanings.

Thermostability means within the framework of this invention that the photocatalytically active metal compounds do not form active components when heated to carry out the polymerization process with ring opening. For example, at room temperature or slightly elevated to about + 40 ^° C, when the light is turned off for several weeks, the catalyst may not initiate ring polymerization. During this time, only a small number of monomers are converted (less than 0.2 wt.%). The thermal stability can be determined, for example, by leaving a toluene solution containing 20 wt.% Of monomer and 0.33 wt.% Of a metal catalyst at a temperature of 50 ^o C for 96 hours in the dark, and possibly the amount of polymer formed, noticeable in the viscous structure and by precipitation in a precipitant, for example ethanol, quantified after filtration and drying, is not more than 0.5 wt.% and preferably not more than 0.2 wt.%.

The claimed compositions advantageously contain the following thermal and / or photochemical one-component catalysts:
1. Thermostable ruthenium or osmium compounds activated due to irradiation, which have at least one photolabile group bonded to the ruthenium or osmium atom and whose other coordination sites are saturated with non-photolabile bound groups.

 As related groups for the ruthenium or osmium compounds used according to the invention, organic or inorganic compounds, atoms or ions are concentrated in the center of the metal.

 A photolabile linked group within the framework of the proposed invention means that when a catalyst is exposed to light in the visible eye or in the ultraviolet spectral region, the bound group dissociates from the catalyst and forms a catalytically active component for metathesis merization. According to the invention, nonionic photolabile linked groups are most preferred.

With respect to photolabile linked groups, for example, nitrogen (N ₂ ), unsubstituted or substituted OH, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₆ -C ₁₂ aryl or monocyclic halogen, polycyclic or fused arenas with carbon atoms in an amount of from 6 to 24, preferably from 6 to 18 and most preferably from 6 to 12, or unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen monocyclic heteroarenes , fused heteroarenes, or fused areo heteroarenes with carbon atoms and in an amount of from 3 to 22, preferably from 4 to 16, and most preferably from 4 to 10 and with one to three heteroatoms selected from the group O, S and N; or unsubstituted or substituted with C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxyl or halogen aliphatic, cycloaliphatic, aromatic or araliphatic nitriles with carbon atoms in an amount of from 1 to 22, preferably from 1 to 18, most preferably from 1 up to 12, and most preferably from 1 to 7. The most preferred substituents are methyl, ethyl, methoxyl, ethoxyl, fluorine, chlorine and bromine. Arenas and heteroarenes are preferably substituted with one or two radicals and most preferably are not substituted. Among heteroarenes, electron-rich heteroarenes are most preferred. Arenas and heteroarenes can have both π- and σ-bonds; in the latter case, the corresponding radicals are aryl and heteroaryl. Aryl preferably contains from 6 to 18 and most preferably from 6 to 12 carbon atoms. Heteroaryl preferably contains from 4 to 16 carbon atoms.

 Some examples of arenes and heteroarenes are benzene, p-cumene, biphenyl, naphthalene, anthracene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene, fluorantrene, furan, thiophene, pyrrole, pyridine, γ-pyran, γ-thiopyran, pyrimidine, pyrazine, indole, kumaron, thionaphtene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline, acridine, chromene, phenazine, phenoxazine, triazine, thiazin, thiazin, thiazin, thiazin, thiazin, thiazin, thiazin, thiazin, thiazin, thiazin, thiazin, thiazin, thiazin. The most preferred arenes and heteroarenes are benzene, naphthalene, thiophene and benzthiophene. Especially preferred are benzene and heteroarene thiophene.

Nitriles can be substituted, for example, with methoxyl, ethoxyl, fluorine or chlorine, it is better if the nitriles are not substituted. Alkyl nitriles preferably have a normal chain. Some examples of nitriles are acetonitrile, propionitrile, butyronitrile, pentyl nitrile, hexyl nitrile, cyclopentyl and cyclohexyl nitrile, benzonitrile, methyl benzonitrile, benzyl nitrile and naphthyl nitrile. Regarding nitriles, C ₁ -C ₄ alkyl nitrile or normal chain benzonitrile are preferred.

As for the photolabile linked groups of the preferred subgroup, we are talking about N ₂ unsubstituted or substituted with one to three C ₁ -C ₄ -alkyl benzene, thiophene, benzonitrile or acetonitrile.

 A non-labile linked group (also referred to as an intensely coordinating linked group) means within the framework of the proposed invention that when a catalyst is irradiated in the visible eye or in the near ultraviolet spectral region, it does not dissociate from the catalyst or dissociates to a small extent.

As for non-photolabile linked groups, we can speak, for example, of inorganic and organic compounds containing and solvating heteroatoms O, S or N, often also used as solvents, or unsubstituted or substituted with C ₁ -C ₄ alkyl, C ₁ - C ₄ alkoxy, (C ₁ -C ₄ alkyl) ₃ Si or (C ₁ -C ₄ alkyl) ₃ SiO cyclopentadienyl or indenyl. Examples of such compounds are H ₂ O, H ₂ S, NH ₃ ; optionally halogenated, in particular fluorinated or chlorinated aliphatic or cycloaliphatic alcohols or mercaptans with carbon atoms in an amount of from 1 to 18, preferably from 1 to 12 and most preferably from 1 to 6, aromatic alcohols or thiols with carbon atoms in an amount of from 6 to 18, preferably from 6 to 12, araliphatic alcohols or thiols having from 7 to 18, preferably from 7 to 12 carbon atoms, aliphatic, cycloaliphatic, araliphatic or aromatic ethers, thioethers ryrs, sulfoxides, sulfones, ketones, aldehydes, carboxylic esters, lactones, optionally NC ₁ -C ₄ monoalkylated or dialkylated alkyl amides of carboxylic acids having from 2 to 20, preferably from 2 to 12 and most preferably from 2 to 6 carbon atoms, and optionally NC ₁ C ₄ -alkylated lactams; aliphatic, cycloaliphatic, araliphatic or aromatic primary, secondary or tertiary amines having from 1 to 20, preferably from 1 to 12 and most preferably from 1 to 6 carbon atoms; and in known cases cyclopentadienyls, such as, for example, cyclopentadienyl, indenyl, one or more methylated or trimethylsilylated cyclopentadienyls or indenyls.

 Examples of such non-photolabile linked groups are methanol, ethanol, n- and i-propanol, n-, i- and t-butanol, 1,1,1-trifluoroethanol, bistrifluoromethylmethanol, tristrifluoromethylmethanol, pentanol, hexanol, methyl or ethyl mercaptan, cyclopentanol, cyclohexanol, cyclohexyl mercaptan, phenol, methylphenol, fluorophenol, phenyl mercaptan, benzyl mercaptan, benzyl alcohol, diethyl ether, simple diisopropyl ether, simple di-n- or di-t-butyl ether, tetrahydrofuran, diethyl ether, tetrahydrofuran, tetrahydrofuran, di-tetrahydrofuran, di-tetrahydrofuran, thioether, etrahydrothiophene, dimethyl sulfoxide, diethyl sulfoxide, tetra- and pentamethylene sulfoxide, dimethyl sulfone, diethyl sulfone, tetra and pentamethylene sulfone, acetone, methyl ethyl ketone, diethyl ketone, ethyl benzyl acetone, benzene, benzene, benzene, benzene dimethylformamide, dimethylacetamide, pyrrolidone and N-methylpyrrolidone, indenyl, cyclopentadienyl, methyl or dimethyl or pentamethylcyclopentadienyl and trimethylsilyl cyclop ntadienil.

Primary amines may correspond to the formula R ₂₅ NH ₂ , secondary amines to the formula R ₂₅ R ₂₆ NH and tertiary amines to the formula R ₂₅ R ₂₆ R ₂₇ N, where R ₂₅ is C ₁ -C ₁₈ alkyl, unsubstituted or substituted by C ₁ -C ₄ -alkyl or C ₁ -C ₄ alkoxyl C ₅ - or C ₆ -cycloalkyl, or unsubstituted or substituted with C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxyl C ₆ -C ₁₈ aryl or C ₇ -C ₁₂ aralkyl, R ₂₆ is independently R ₂₅ , or R ₂₅ and R ₂₆ are together tetramethylene, pentamethylene, 3-oxa-1,5-pentylene or —CH ₂ —CH ₂ —NH — CH ₂ —CH ₂ - or -CH ₂ -CH ₂ -N (C ₁ -C ₄ -alkyl) -CH ₂ -CH ₂ -, R ₂₅ and R _{26 are} independently of the above values, and R ₂₇ has its own value of R ₂₅ . Alkyl preferably contains from 1 to 12, and most preferably from 1 to 6 carbon atoms. Aryl preferably contains from 6 to 12 carbon atoms, and aralkyl preferably from 7 to 9 carbon atoms. Examples of amines are methyl, dimethyl, trimethyl, ethyl, diethyl, triethyl, methyl ethyl, dimethyl ethyl, n-propyl, di-n-propyl, tri-n-butyl, cyclohexyl-, phenyl- and benzylamine, as well as pyrrolidine, N-methylpyrrolidine, piperidine, piperazine, morpholine and N-methylmorpholine.

With respect to the non-photolabile linked groups, one of the preferred subgroups is H ₂ O, NH ₃ and unsubstituted or partially or fully fluorinated C ₁ -C ₄ alkanols. Particular preference is given to H ₂ O, NH ₃ , cyclopentadienyl, methanol and ethanol.

где Lig стоит вместо фотолабильных связанных групп, a Me вместо рутения или осмия, A₉, A₁₀ и A₁₁ представляют двухвалентную мостиковую группу, а Y^⊖ обозначает одновалентный некоординирующий анион. Мостиковая группа является предпочтительно ионной, наиболее предпочтительно это галогенид, лучше всего хлористое, бромистое или иодистое соединение. В отношении фотолабильной связанной группы речь идет предпочтительно об одинаковых или разных аренах, аY^⊖ может представлять приведенные далее анионы и в особенности хлористое, бромистое или иодистое соединение. Примером таких комплексов служит [C₆H₆Ru(Cl)₃RuC₆H₆]Cl.Regarding the compounds of ruthenium and osmium used according to the invention, one can speak of single-core or multi-core, for example, those that contain two or three metal centers. In this case, metal atoms can be connected using a bridging group or metal-metal bonds. Among compounds having several metal centers, those compounds of formula VIII are most preferred.

where Lig stands for photolabile linked groups, a Me instead of ruthenium or osmium, A ₉ , A ₁₀ and A ₁₁ represent a divalent bridging group, and Y ^⊖ represents a univalent non-coordinating anion. The bridging group is preferably ionic, most preferably a halide, preferably a chloride, bromide or iodide compound. With respect to the photolabile linked group, these are preferably identical or different arenas, and Y ^⊖ may represent the following anions, and in particular the chloride, bromide or iodide compound. An example of such complexes is [C ₆ H ₆ Ru (Cl) ₃ RuC ₆ H ₆ ] Cl.

The most preferred catalysts according to the invention correspond to formula IX
[(Me ^{+ n} ) (L ₁ ^z1 ) _m (L ₂ ^z2 ) _o (L ₃ ^z3 ) _p (L ₄ ^z4 ) _q (L ₅ ^z5 ) _r (L ₆ ^z6 ) _s ]
(L ₇ ^z7 ) _t , (IX)
where Me is ruthenium or osmium;
n is 0, 1, 2, 3, 4, 5, 6, 7, or 8;
L ₁ is a photolabile linked group;
L ₂ , L ₃ , L ₄ , L ₅ and L ₆ independently of one another represent a non-photolabile or photolabile linked group;
m is 1, 2, 3, 4, 5, or 6;
o, p, q, r and s are independently 0, 1, 2, 3, 4 or 5;
z ₁ , z ₂ , z ₃ , z ₄ , z ₅ , z ₆ and z _{7 are} independently -4, -3, -2, -1, 0, +1 or +2; a
L ₇ denotes a non-coordinating cation or anion;
where the sum m + o + p + r + s + q denotes an integer from 2 to 6, at is the coefficient of (n + m • z ₁ + о • z ₂ + р • z ₃ + q • z ₄ + r • z ₅ + s • z ₆ ) / z ₇ .

In the formula IX, L _{7 is} preferably instead of halogen (e.g. chlorine, bromine and iodine), an oxygen acid anion, BF ₄ , PF ₆ , SiF ₆ or AsF ₆ .

With respect to anions of oxygen acids, we can speak, for example, of sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, anion of C ₁ -C ₈ -carboxylic acid, such as formate, acetate, propionate, butyrate benzoate, phenylacetate, mono-, di- or trichloro- or fluoroacetate, sulfonates, such as methyl sulfonate, ethyl sulfonate, propyl sulfonate, butyl sulfonate, trifluoromethyl sulfonate (triflate), optionally substituted with C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen, in particular fluorine, chlorine or bromine f nylsulfonate or benzyl sulfonate, such as tosylate, mesylate, tosylate, p-methoxy or p-ethoxyphenyl sulfonate, pentafluorophenyl sulfonate or 2,4,6-triisopropyl sulfonate, and phosphonates, such as methylphosphonate, ethylphosphonate, propylphosphonate, propylphosphonate, butylphosphonate, propyl, , p-methylphenylphosphonate or benzylphosphonate.

In the formula IX, Me stands preferably instead of ruthenium, in particular instead of Ru ²⁺ .

A particularly noteworthy group of compounds of formula IX is that wherein the ligands L ₁ , L ₂ , L ₃ , L ₄ and L ₅ and L _{6 are} independently unsubstituted or substituted with C ₁ -C ₄ alkyl, C ₁ -C ₄ - alkoxyl or halogen aliphatic, cycloaliphatic, aromatic or araliphatic nitriles having from 1 to 22 carbon atoms, or C ₆ -C ₁₈ aryl; or L ₁ , L ₂ and L ₃ together represent unsubstituted or substituted by —OH, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₆ -C ₁₂ aryl or halogen monocyclic, polycyclic or condensed arenes having from 6 to 24, preferably from 6 to 18, and most preferably from 6 to 12 carbon atoms, or unsubstituted or substituted by —OH, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen monocyclic heteroarenes, fused heteroarenes, or fused arene heteroarenes having from 4 to 22 carbon atoms and from 1 to 3 heteroatoms selected from the group O, S and N, and L ₄ , L ₅ and L ₆ together have the same meaning, or individually, independently of one another, are N ₂ or the aforementioned nitrile or the aforementioned C ₆ -C ₁₈ aryl.

The most preferred subgroup of the above compounds of formula IX is that where the ligands L ₁ , L ₂ , L ₃ , L ₄ , L ₅ and L _{6 are} independently N ₂ , C ₁ -C ₂₀ alkyl nitrile, C ₆ -C ₁₂ aryl nitrile, C ₇ -C ₁₂ aralkyl nitrile, C ₆ -C ₁₂ aryl or L ₁ , L ₂ and L ₃ together represent A ₁ or A ₂ groups.

где R₂₈, R₂₉, R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ и R₃₇ независимо друг от друга обозначают водород, C₁-C₂₀-алкил, C₁-C₂₀-алкоксил, арил или SiR₃₈R₃₉R₄₀, причем в группах A₁ и A₂ у соседних углеродных атомов может конденсироваться ароматическое или гетероароматическое кольцо, гетероатомы которого выбраны из группы кислорода, серы и азота; R₃₈, R₃₉ и R₄₀ независимо друг от друга обозначают C₁-C₁₂-алкил, C₅- или C₆-циклоалкил, или незамещенный или замещенный C₁-C₆-алкилом или C₁-C₆-алкоксилом фенил или бензил, предпочтительно C₁-C₈-алкил, фенил или бензил, наиболее предпочтительно C₁-C₄-алкил, фенил или бензил, a L₄, L₅ и L₆ вместе имеют то же значение или каждый в отдельности представляет N₂, вышеназванные нитрилы или вышеназванный C₆-C₁₂-арил, или обозначают арен или гетероарен.

where R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ and R _{37 are} independently hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ -alkoxyl, aryl or SiR ₃₈ R ₃₉ R ₄₀ , moreover, in groups A ₁ and A ₂ , adjacent aromatic atoms may condense an aromatic or heteroaromatic ring, heteroatoms of which are selected from the group of oxygen, sulfur and nitrogen; R ₃₈ , R ₃₉ and R _{40 are} independently C ₁ -C ₁₂ alkyl, C ₅ or C ₆ cycloalkyl, or unsubstituted or substituted with C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy phenyl or benzyl, preferably C ₁ -C ₈ -alkyl, phenyl or benzyl, most preferably C ₁ -C ₄ -alkyl, phenyl or benzyl, a L ₄ , L ₅ and L ₆ together have the same meaning or each individually represents N ₂ , the aforementioned nitriles or the aforementioned C ₆ -C ₁₂ aryl, or are arenes or heteroarenes.

Of this noteworthy group of compounds of formula IX, preferred are those wherein L ₁ , L ₂ , L ₃ , L ₄ , L ₅ and L _{6 are} independently C ₁ -C ₁₂ alkylnitrile, C ₆ -C ₁₂ aryl nitrile or L ₁ , L ₂ and L ₃ represent groups A ₁ and A ₂ , and L ₄ , L ₅ and L ₆ also together have the same meaning or individually represent N ₂ , the above nitriles or the above arene or heteroarene of the formulas A ₁ and A ₂ , where R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ and R _{37 are} independently of each other instead of hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ -alkoxyl, SiR ₃₈ R ₃₉ R ₄₀ or phenyl, moreover, in groups A ₁ and A ₂ at of the adjacent carbon atoms, a benzene ring may condense, and R ₃₈ , R ₃₉ and R ₄₀ are methyl, ethyl or phenyl.

In one of the most preferred embodiments of the inventive method, the catalyst used corresponds to formula IX, where L ₁ , L ₂ , L ₃ , L ₄ , L ₅ and L _{6 are} independently methyl nitrile, ethyl nitrile or phenyl nitrile, or L ₁ , L ₂ and L ₃ together represent groups A ₁ or A ₂ , and L ₄ , L ₅ and L ₆ also together have the same meaning or individually represent the above nitriles, where R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ and R _{37 are} independently of each other instead of hydrogen, methyl, methoxy or phenyl, and in groups A ₁ and A ₂ at adjacent carbon atoms can condense the benzene ring.

Another most preferred subgroup of compounds of formula IX is where L ₁ , L ₂ and L ₃ together are unsubstituted or substituted with C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₆ -C ₁₂ aryl or halogen monocyclic , polycyclic or condensed arenes having from 6 to 24, preferably from 6 to 18 and most preferably from 6 to 12 carbon atoms, or unsubstituted or substituted by C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxyl or halogen monocyclic heteroarenes fused heteroarenes or fused areo heteroarenes have from 4 to 22, preferably from 4 to 16, and most preferably from 4 to 10 carbon atoms and from 1 to 3 heteroatoms selected from the group O, S and N, a L ₄ , L ₅ and L ₆ denotes a non-photolabile linked group, and here the above preference is given.

L ₁ , L ₂ and L ₃ are preferably benzene or naphthalene in this subgroup, and non-photolabile ligands are preferably H ₂ O, NH ₃ unsubstituted or substituted by fluorine C ₁ -C ₄ alkanol or C ₁ -C ₄ alkanethiol, aliphatic ethers, thioether, sulfoxides or sulfones with carbon atoms in an amount of from 2 to 8, dimethylformamide or N-methylpyrrolidone.

The following preferred subgroup of compounds of formula X deals with ruthenium and osmium compounds of formula X
[L ₁ Me (L ₈ ) ₅ ] ^2⊕ [Y $\genfrac{}{}{0ex}{}{\text{x⊖}}{\text{1}}$ ] _{2 / x} (X)
where L ₁ is a photolabile linked group, L ₈ is a non-photolabile linked group, Me is ruthenium or osmium, Y ₁ is a non-coordinating anion, and x stands for integers 1, 2 or 3. Photolabile, non-photolabile ligands, Me and Y _{1 are} given above preference. Most preferred is L ₁ N ₂ or nitrile, such as, for example, C ₁ -C ₄ alkyl nitrile (acetonitrile), benzonitrile or benzyl nitrile, L ₈ NH ₃ or an amine with carbon atoms in an amount of from 1 to 12, Y _{1 is a} non-coordinating anion, and x is the number 1 or 2.

For the proposed invention, the most suitable catalysts are the following (tos is tosylate, and tis is 2,4,6-triisopropyl phenyl sulfonate):
Ru (CH ₃ CN) ₆ (tos) ₂ ,
Ru (CH ₃ CH ₂ CN) ₆ (tos) ₂ ,
Ru (CH ₃ CN) ₆ (CF ₃ SO ₃ ) ₂ ,
Ru (CH ₃ CH ₂ CN) ₆ (CF ₃ SO ₃ ) ₂ ,
Ru (C ₆ H ₆ ) ₂ (tos) ₂ ,
[Ru (C ₆ H ₆ ) (C ₆ H ₅ OCH ₃ )] (BF ₄ ) ₂ ,
[Ru (C ₆ H ₆ ) (C ₆ H ₅ i-propyl)] (BF ₄ ) ₂ ,
[Ru (C ₆ H ₆ ) (1,3,5-trimethylphenol] (BF ₄ ) ₂ ,
[Ru (C ₆ H ₆ ) - (hexamethylbenzene)] (BF ₄ ) ₂ ,
[Ru (C ₆ H ₆ ) (biphenyl)] (BF ₄ ) ₂ ,
[Ru (C ₆ H ₆ ) (chrysene)] (BF ₄ ) ₂ ,
[Ru (C ₆ H ₆ ) (naphthalene)] (BF ₄ ) ₂ ,
[Ru (cyclopentadienyl) (4-methylcumyl)] PF ₆ ,
[Ru (cyanophenyl) ₆ ] (tos) ₂ ,
[Ru (cyanophenyl) ₆ ] (CF ₃ SO ₃ ) ₂ ,
[Ru (C ₆ H ₆ ) (tetramethylthiophene) ₃ ] (tos) ₂ ,
[Ru (C ₆ H ₆ ) (CH ₃ CN) ₃ ] (tos) ₂ ,
[Ru (C ₆ H ₆ ) (tetramethylthiophene) ₃ ] (CF ₃ SO ₃ ) ₂ ,
[Ru (C ₆ H ₆ ) (CH ₃ CN) ₃ ] (CF ₃ SO ₃ ) ₂ ,
[Ru (C ₆ H ₆ ) (CH ₃ OH) ₃ ] (tos) ₂ ,
[Ru (C ₆ H ₆ ) (CH ₃ OH) ₃ ] (tis) ₂ ,
[Os (NH ₃ ) ₅ N ₂ ] (PF ₆ ) ₂ ,
[Ru (NH ₃ ) ₅ N ₂ ] (PF ₆ ) ₂ ,
[Ru (NH ₃ ) ₅ (CH ₃ CN)] (BF ₄ ),
[Ru (C ₆ H ₆ (NH ₃ ) ₃ ] (tis) ₂ ),
[Ru (C ₆ H ₆ (tetrahydroteophen) ₃ ] (CF ₃ SO ₃ ) ₂ ,
[Ru (CH ₃ ) ₂ S) ₃ C ₆ H ₆ ] (tos) ₂ ,
[Ru (dimethyl sulfoxide) ₃ C ₆ H ₆ ] (PF ₆ ) ₂ ,
[Ru (dimethylformamide) ₃ C ₆ H ₆ ] - (PF ₆ ) ₂ ,
[Ru (C ₆ H ₆ ) Cl ₂ ] ₂ ,
[Os (C ₆ H ₆ ) Cl ₂ ] ₂ .

 The ruthenium and osmium catalysts used according to the invention are either known and partially obtained in the process, or obtained by analogy with known methods. Such catalysts and their preparation are described, for example, in Gilkerson, W.R., Jackson. M.D., J. Am. Chem. Soc. 1O1: 4096-411 (1979), Bennett, M. A., Matheson. T.W., J. Organomet. Chem. 175: 87-93 (1979), Moorehouse, S., Wilkinson, G., J. Chem. Soc .; Dalton Trans., 2187-2190 (1974) u Luo. S., Rauchfuss, T. B., Wilson, S. R., J. Am. Chem. Soc. 114: 8515-8520 (1992).

 2. Thermostable compounds of molybdenum (VI) or tungsten (VI), capable of being activated by increasing temperature or under the influence of light rays, containing at least two methyl groups or two monosubstituted methyl groups associated with the metal, the substituent not containing a hydrogen atom in position α.

The remaining valencies of molybdenum and tungsten are preferably saturated with thermostable neutral ligands, which are known in large quantities. The number of neutral linked groups may also exceed the stoichiometrically possible number (solvates). Thermostability is described above. At temperatures above 50 ^o C, for example from 60 to 300 ^o C, these molybdenum and tungsten compounds are also thermally activated.

With respect to the compounds of molybdenum and tungsten used according to the claimed invention, we can talk about such compounds that contain one metal atom or two metal atoms connected by a simple, double or triple bond. A metal-bonded methyl group or a monosubstituted methyl group is bonded at least twice, preferably 2 to 6 times, and most preferably 2 to 4 times. Such a linked group preferably corresponds to formula XI,
-CH ₂ -R, (XI)
where R is hydrogen, —CF ₃ , —SiR ₃₈ R ₃₉ R ₄₀ , —CR ₄₁ R ₄₂ R ₄₃ , unsubstituted or substituted with C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxyl C ₆ -C ₁₆ aryl or C ₄ -C ₁₅ heteroaryl with one to three heteroatoms from the group O, S and N; and R ₄₁ , R ₄₂ and R _{43 are} independently C ₁ -C ₁₀ alkyl which is substituted with C ₁ -C ₁₀ alkoxyl or not substituted, or R ₄₁ and R ₄₂ have the same meaning and R ₄₃ is C ₆ -C ₁₀ aryl or C ₄ -C ₉ heteroaryl which is unsubstituted or substituted by C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy; and R ₃₈ , R ₃₉ and R ₄₀ have the above meanings.

If R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ and R ₄₃ are alkyl, then it may have a straight or branched chain and preferably from 1 to 8 and most preferably from 1 to 4 carbon atoms. If R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ and R ₄₃ are aryl, it is preferably phenyl or naphthyl.

 If R in the formula XI is aryl, then it is preferably phenyl or naphthyl. If R in the formula XI is heteroaryl, then it is preferably pyridinyl, furanyl, thiophenyl or pyrrolyl.

The most preferred substituents for R ₃₈ -R ₄₃ are, within the definitions, methyl, ethyl, methoxy or ethoxyl. Examples for radicals R ₃₈ -R ₄₃ are given above with reference to compounds of formula I.

In one preferred embodiment of the invention, the group R in formula XI is hydrogen, —C (CH ₃ ) ₃ , —C (CH ₃ ) ₂ C ₆ H ₅ unsubstituted or substituted with methyl, ethyl, methoxy or ethoxy phenyl, —CF ₃ or -Si (CH ₃ ) ₃ .

The remaining valencies of the molybdenum (VI) and tungsten (VI) atoms are, if necessary, saturated with the same or different ligands from the group = O, = NR ₄₄ , secondary amines with 2-18 carbon atoms, R ₄₅ O-, R ₄₅ S-, halogen, if necessary substituted cyclopentadienyl, bridged biscyclopentadienyl, trident single anionic ligands and neutral ligands, such as, for example, ethers, nitriles, CO and tertiary phosphines and amines, where R _{45 is} independently unsubstituted or substituted with C ₁ -C ₆ alkoxy or halogen C ₁ -C ₁₈ -alkyl rate noy or branched chain, unsubstituted or substituted C ₁ -C ₆ -alkyl, C ₁ -C ₆ alkoxy or halogen, C ₅ - or C ₆ -cycloalkyl, unsubstituted or substituted C ₁ -C ₆ -alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxymethyl, C ₁ -C ₆ alkoxyethyl or halogen phenyl, or unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxymethyl, C ₁ -C ₆ alkoxyethyl or halogen benzyl or phenylethyl; and R ₄₄ represents an unsubstituted or substituted C ₁ -C ₆ alkoxy C ₁ -C ₁₈ alkyl linear or branched chain, unsubstituted or substituted C ₁ -C ₆ -alkyl, C ₁ -C ₆ alkoxy or halogen, C ₅ - or C ₆ -cycloalkyl unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxymethyl, C ₁ -C ₆ alkoxyethyl, C ₁ -C ₆ dialkylamino, C ₁ -C ₆ dialkylamino-C ₁ -C ₃ -alkyl or halogen phenyl, or unsubstituted or substituted by C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxyl, C ₁ -C ₆ -alkoxymethyl, C ₁ -C _6- alkoxyethyl or halogen benzyl or phenylethyl.

Secondary amines are preferably those amines of the formula R ₄₆ R ₄₇ N-, where R ₄₆ and R _{47 are,} independently of one another, straight or branched chain C ₁ -C ₁₈ alkyl; C ₅ or C ₆ cycloalkyl; unsubstituted or substituted with C ₁ -C ₆ alkoxyl or halogen benzyl or phenylethyl or (C ₁ -C ₆ alkyl) ₃ Si; or R ₄₆ and R ₄₇ together are tetramethylene, pentamethylene or 3-oxapentane-1,5-diyl. Alkyl preferably contains from 1 to 12 and most preferably from 1 to 6 carbon atoms. Some examples are dimethyl, diethyl, di-n-propyl, di-i propyl, di-n-butyl, methylethyl, dibenzyl, benzylmethyl, diphenyl, phenylmethylamino and di (trimethylsilyl) amino .

 Halogen as a linked group or substituent is preferably fluorine or chlorine, most preferably chlorine.

Cyclopentadienyl may be unsubstituted or substituted one to five times by C ₁ -C ₄ alkyl, especially methyl, or -Si (C ₁ -C ₄ -alkyl), especially -Si (CH ₃ ) ₃ .

Bridged cyclopentadienyls are, in particular, those in the formula R ₄₈ —AR ₄₈ where R ₄₈ is one to five times unsubstituted or substituted with C ₁ -C ₄ alkyl, especially methyl, or —Si (C ₁ -C ₄ -alkyl), especially -Si (CH ₃ ) ₃ cyclopentadienyl, and A stands in place of -CH ₂ , -CH ₂ -CH ₂ -, -Si (CH ₃ ) ₂ -, -Si (CH ₃ ) ₂ -Si (CH ₃ ) ₂ - or -Si (CH ₃ ) ₂ -O-Si (CH ₃ ) ₂ -.

 Regarding ethers as neutral bound groups, we can talk about a simple dialkyl ether, which contains from 2 to 8 carbon atoms, or a cyclic ether, which contains 5 or 6 ring elements. Some examples are diethyl ether, methylethyl, diethyl, n-dipropyl, i-dipropyl, n-dibutyl, ethylene glycol dimethyl ethers, tetrahydrofuran and dioxane.

 With respect to nitriles as neutral linked groups, one can speak of aliphatic or aromatic nitriles with carbon atoms in an amount of from 1 to 12, preferably from 1 to 8. Some examples are acetonitrile, propionitrile, butyl nitrile, benzonitrile and benzyl nitrile.

 With regard to tertiary amines and phosphates as neutral linked groups, we can talk about those that contain from 3 to 24, preferably from 3 to 18 carbon atoms. Some examples are trimethylamine and trimethylphosphine, triethylamine and triethylphosphine, n-tripropylamine and α-phosphine, n-tributylamine and α-phosphine, triphenylamine and α-phosphine, tricyclohexylamine and α-phosphine, phenyl dimethyl amine and α-phosphine, benzyl dimethyl dimethyl dimethyl dimethyl amine dimethylamine and 3,3-dimethylphenyl-dimethylphosphine.

, где R' обозначает водород или метил, а R₅₀, как и R₅₁, независимо друг от друга обозначают C₁-C₄-алкил, C₁-C₄-алкоксил или фенил (см. Klaui, W., Angew. Chem. 102:661-670 (1990).With respect to trident single anionic linked groups, for example, hydro (trispyrazol-1-yl) borates or alkyl- (trispyrazol-1-yl) borates, which are unsubstituted or substituted from one to three times by C ₁ -C ₄ -alkyl ( see Trofimenko, S., Chem. Rev. 93: 943-980 (1993), or o

where R 'is hydrogen or methyl, and R ₅₀ , like R ₅₁ , are independently C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or phenyl (see Klaui, W., Angew. Chem. 102: 661-670 (1990).

With respect to halogens as substituents for the radicals R ₄₄ and R _45, it is primarily a question of fluorine and most preferably chlorine. The substituents alkyl, alkoxyl or alkoxyl in alkoxymethyl or alkoxyethyl preferably contain from 1 to 4 and most preferably from 1 to 2 carbon atoms. Examples are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, methoxy, ethoxyl, n- and i-propyloxy and n-, i- and t-butyloxyl.

R ₄₄ and R ₄₅ , denoting alkyl, preferably contain from 1 to 12, most preferably from 1 to 8, and most preferably from 1 to 4 carbon atoms. It is preferably a branched chain alkyl. Some examples of R ₄₄ are methoxyl, ethoxyl, n- and i-propyloxy, n-, i- and t-butyloxy i-hexafluoropropyloxy and hexa-, as well as perfluorobutyloxy.

Some examples of substituted phenyl and benzyl for R ₄₄ and R ₄₅ are p-methylphenyl or benzyl, p-fluoro or p-chlorophenyl or benzyl, p-ethylphenyl or benzyl, pn- or i-propylphenyl or benzyl, pi- butylphenyl or -benzyl, 3-methylphenyl or -benzyl, 3-i-propylphenyl or -benzyl, 2,6-dimethylphenyl or -benzyl, 2,6-di-i-propylphenyl or -benzyl, 2,6-di-n - or -t-butylphenyl or -benzyl. R _{45 is} most preferably substituted for unsubstituted or substituted C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy phenyl.

где Me стоит вместо молибдена (VI) или вольфрама (VI); по меньшей мере два, предпочтительно от 2 до 4 остатков R₅₃-R₅₈ обозначают радикал -CH₂-R формулы XI, где R имеет вышеприведенное значение; остальные радикалы R₅₃-R₅₈ обозначают попарно = O или =N-R₄₄, а R₄₄ имеет вышеприведенное значение; и/или остальные радикалы R₅₃-R₅₈ обозначают вторичные аминогруппы с углеродными атомами в количестве от 2 до 18, R₄₅O- или R₄₅S-, галоген, циклопентадиенил или бисциклопентадиенил с мостиковой связью или нейтральную связанную группу, где R₄₅ имеет вышеприведенное значение. Радикалам R и R₃₈-R₄₅ отдается вышеуказанное предпочтение.In one preferred embodiment of the invention, the compounds of molybdenum and tungsten correspond especially to one of formulas XII - XIIc

where Me stands in place of molybdenum (VI) or tungsten (VI); at least two, preferably from 2 to 4, residues R _{53 to} R ₅₈ represent the radical —CH ₂ —R of formula XI, where R is as defined above; the remaining radicals R ₅₃ -R ₅₈ denote pairwise = O or = NR ₄₄ , and R ₄₄ has the above meaning; and / or other radicals R ₅₃ -R ₅₈ denote secondary amino groups with carbon atoms in an amount of from 2 to 18, R ₄₅ O- or R ₄₅ S-, halogen, cyclopentadienyl or biscyclopentadienyl with a bridged bond or a neutral linked group, where R ₄₅ has the above value. The radicals R and R ₃₈ -R _{45 are} given the above preference.

In one of the most preferred embodiments of the invention, the claimed composition uses molybdenum or tungsten compounds of the formula XII, where
a) R ₅₃ -R ₅₈ denote a radical of the formula XI-CH ₂ -R, or
b) R ₅₃ and R ₅₄ represent a radical of the formula XI —CH ₂ —R, R ₅₅ and R ₅₆ together represent a radical = NR ₄₄ , and R ₅₇ and R ₅₈ together independently represent R ₄₅ —O or halogen, or
c) R ₅₃ and R ₅₄ together and R ₅₅ and R ₅₆ together represent a radical = NR ₄₄ , and R ₅₇ and R ₅₈ represent a radical of the formula XI —CH ₂ —R,
wherein R, R ₄₄ and R ₄₅ are as defined above. R, R ₄₄ and R _{45 are} preferred, as stated above.

Among the compounds of formula XIIc, particular preference is given to those in which R ₅₃ , R ₅₄ and R ₅₅ denote a radical of formula XI, with respect to the radical of formula XI, -CH ₂ -Si (C ₁ -C ₄ -alkyl) ₃ is preferred.

где Me стоит вместо молибдена (VI) или вольфрама (VI),
R представляет водород, -C(CH₃)₃, -C(CH₃)₂-C₆-H₅, -C₆H₅ или (C₁-C₄-алкил)₃,
R₆₃ обозначает фенил или фенил, замещенный 1-3 раза C₁-C₄-алкилом или C₁-C₄-алкоксилом,
R₅₃ представляет незамещенный или замещенный фтором C₁-C₄-алкоксил с нормальной или разветвленной цепью, и
R₅₄ имеет то же значение, что и R₅₃ или стоит вместо фтора, хлора или брома. R₅₃ представляет наиболее предпочтительно алкоксил с разветвленной цепью, который при необходимости замещен частично или полностью фтором, например i-пропилоксил, i- и t-бутилоксил, гексафторпропилоксил и нонафтоpпропилоксил. В отношении R₅₄ речь идет предпочтительно о хлоре.In the claimed composition is best used compounds of molybdenum or tungsten of the formulas XII, XIIIa or XIIIb,

where Me stands in place of molybdenum (VI) or tungsten (VI),
R is hydrogen, —C (CH ₃ ) ₃ , —C (CH ₃ ) ₂ —C ₆ —H ₅ , —C ₆ H ₅ or (C ₁ -C ₄ alkyl) ₃ ,
R ₆₃ is phenyl or phenyl substituted 1-3 times with C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxyl,
R ₅₃ represents a straight or branched chain unsubstituted or fluorine substituted C ₁ -C ₄ alkoxyl, and
R ₅₄ has the same meaning as R ₅₃ or stands instead of fluorine, chlorine or bromine. R ₅₃ is most preferably a branched chain alkoxyl which is optionally substituted partially or completely with fluorine, for example i-propyloxy, i- and t-butyloxy, hexafluoropropyloxy and nonaphthopropyloxy. With respect to R _54, it is preferably chlorine.

Some examples of molybdenum and tungsten compounds are:
W (= NC ₆ H ₅ ) (OC (CH ₃ ) ₃ (Cl) [(CH ₂ Si (CH ₃ ) ₃ )] ₂ ,
W (= NC ₆ H ₅ ) (OC (CF ₃ ) ₂ CH ₃ ) ₂ [(CH ₂ Si (CH ₃ ) ₃ )] ₂ ,
[(CH ₃ ) ₃ SiCH ₂ ] ₃ Mo = Mo [CH ₂ Si (CH ₃ ) ₃ ] ₃ ,
W (= NC ₆ H ₅ ) [(CH ₂ Si (CH ₃ ) ₃ )] ₂ Cl,
Mo (= N-2,6-dimethylC ₆ H ₅ ) ₂ [(CH ₂ -C ₆ H ₅ )] ₂ ,
W [2,6- (CH ₃ ) ₂ C ₆ H ₃ N] ₂ (CH ₂ -C ₆ H ₅ ) ₂ ,
Mo (= N-2,6-diisopropylC ₆ H ₃ ) ₂ [(CH ₂ -C ₆ H ₅ )] ₂ ,
Mo (= N-2,6-diisopropylC ₆ H ₃ ) ₂ [(CH ₂ C (CH ₃ ) ₂ -C ₆ H ₅ ] ₂ and
Mo (= N-2,6-dimethylC ₆ H ₃ ) ₂ (CH ₃ ) ₂ (tetrahydrofuran).

 The molybdenum and tungsten catalysts used according to the invention are known and are obtained by known and similar methods from compounds containing a metal halide group using the Grignard reaction (see, for example, Hug, F., Mowat, W., Shortland. A., Skapski., AC , Wilkinson, G., J. Chem. Soc., Chem. Commun. 1079-1080 (1971) or Schrock. RR, Murdzeck, JS, Basan, GC, Robbins, J., DiMare.M., O'Regan, M., J. Am. Chem. Soc. 112: 3875-3886 (1990).

 3. Thermostable compounds of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI), in which the silylmethyl group and at least one halogen are bonded to the metal. These one-component catalysts have particular photocatalytic activity.

With respect to the compounds of the invention used in accordance with the invention, titanium (IV), niobium (V) and tantalum (V) compounds are mentioned which contain a metal atom. In relation to the claimed compounds of molybdenum (VI) and tungsten (VI) we can talk about those that contain a metal atom or two metal atoms that are connected by a simple, double or triple bond. The remaining valencies of titanium, niobium, tantalum, molybdenum and tungsten are preferably saturated with thermostable neutral ligands, and the definition of thermal stability has already been given above. With respect to the metal-bonded halogen, it is preferably said fluorine, chlorine, bromine and iodine, most preferably fluorine, chlorine and bromine, and most preferably fluorine or chlorine. The silylmethyl linked group preferably corresponds to formula XIV,
-CH ₂ -SiR ₃₈ R ₃₉ R ₄₀ , (XIV)
where R ₃₈ , R ₃₉ and R _{40 are} independently C ₁ -C ₁₈ alkyl, C ₅ or C ₆ cycloalkyl or unsubstituted or substituted with C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy phenyl or benzyl.

If R ₃₈ -R ₄₀ is alkyl, then it may have a straight or branched chain and preferably contain from 1 to 12, most preferably from 1 to 8, and preferably from 1 to 4 carbon atoms. Most preferred alkyl is methyl and ethyl.

Phenyl and benzyl, as preferred substituents for R ₃₈ -R ₄₀ , are defined as methyl, ethyl, methoxy and ethoxyl.

In one preferred embodiment of the invention, in a group of formula XIV, R ₃₈ -R ₄₀ are C ₁ -C ₄ alkyl, phenyl or benzyl.

Some examples for a group of formula XIV are —CH ₂ —Si (CH ₃ ) ₃ , —CH ₂ —Si (C ₂ H ₅ ) ₃ , —CH ₂ —Si (nC ₃ H ₇ ) ₃ , —CH ₂ —Si ( n- C ₄ H ₉ ) ₃ , -CH ₂ -Si (CH ₃ ) ₂ (nC ₄ H ₉ ),
—CH ₂ —Si (CH ₃ ) ₂ (tC ₄ H ₉ ), —CH ₂ —Si (CH ₃ ) ₂ (C ₂ H ₅ ), —CH ₂ —Si (CH ₃ ) ₂ [C (CH ₃ ) ₂ CH (CH ₃ ) ₂ ], -CH ₂ -Si (CH ₃ ) ₂ - (nC ₁₂ H ₂₅ ), -CH ₂ -Si (CH ₃ ) ₂ (nC ₁₈ H ₃₇ ), -CH ₂ -Si ( C ₆ H ₅ ) ₃ , -CH ₂ - Si (CH ₂ -C ₆ H ₅ ) ₃ , -CH ₂ -Si (C ₆ H ₅ ) (CH ₃ ) ₂ and -CH ₂ -Si (CH ₂ -C ₆ H ₅ ) (CH ₃ ) ₂ . Most preferred is —CH ₂ —Si (CH ₃ ) ₃ .

The remaining valencies of the atoms of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) and tungsten (VI) are optionally saturated with the same or different neutral ligands, for example, selected from the group consisting of = O, = NR ₄₄ , secondary amines with 2-18 carbon atoms, R ₄₅ O-, R ₄₅ S-, halogen, optionally substituted cyclopentadienyl, bridged biscyclopentadienyl, trident single anionic linked groups and neutral linked groups such as, for example, ethers, nitriles, CO and tertiary phosphines and amines, wherein R ₄₅ denotes independent of one another unsubstituted or substituted C ₁ -C ₆ alkoxy or halo C ₁ -C ₁₈ alkyl linear or branched chain, unsubstituted or substituted C ₁ -C ₆ -alkyl, C ₁ -C ₆ alkoxy or halo C ₅ or C ₆ cycloalkyl unsubstituted or substituted by C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxymethyl, C ₁ -C ₆ alkoxyethyl or halogen phenyl, or unsubstituted or substituted C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxymethyl, C ₁ -C ₆ alkoxyethyl or halogen benzyl or phenylethyl; and R ₄₄ is unsubstituted or substituted C ₁ -C ₆ alkoxyl C ₁ -C ₁₈ straight or branched chain alkyl, unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxyl or C ₅ - halogen or C ₆ -cycloalkyl unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxymethyl, C ₁ -C ₆ alkoxyethyl, C ₁ -C ₆ dialkylamino, C ₁ -C ₆ dialkylamino-C ₁ -C ₃ -alkyl or halogen phenyl, or unsubstituted or substituted by C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxyl, C ₁ -C ₆ -alkoxymethyl, C ₁ -C _6- alkoxyethyl or halogen benzyl or phenylethyl, with the proviso that in taking into account the titanium compound, the ligand is not = O or = NR ₄₄ .

The meanings and preference of R ₄₄ and R ₄₅ , secondary amines, halogen as the next group attached to a metal atom or as a substituent, cyclopentadienyl, ethers, nitriles, tertiary amines and phosphines as neutral ligands and trident single anionic ligands were given above. The meanings and preference given to alkyl, alkoxyl or alkoxyl as a substituent in alkoxymethyl or alkoxyethyl are also given above.

где Me₁ стоит вместо ниобия (VI) или тантала (VI);
Me₂ стоит вместо ниобия (V) или тантала (V);
один из радикалов R₆₉-R₇₄ обозначает радикал -CH₂-SiR₃₈R₃₉R₄₀ формулы XIV;
по меньшей мере один из радикалов R₆₉-R₇₄ представляет фтор, хлор или бром;
R₃₈, R₃₉ и R₄₀ независимо друг от друга обозначают C₁-C₆-алкил, C₅- или C₆-циклоалкил, или незамещенный или замещенный C₁-C₆-алкилом или C₁-C₆-алкоксилом фенил или бензил;
в формуле XV два или в определенный момент два, а в формуле XVa два из оставшихся радикалов R₆₉-R₇₄ вместе обозначают =O или =N-R₄₄, a R₄₄ представляет незамещенный или замещенный C₁-C₆-алкоксилом C₁-C₁₈-алкил с нормальной или разветвленной цепью, незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом или галогеном C₅- или C₆-циклоалкил, незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом, C₁-C₆-алкоксиметилом, C₁-C₆-алкоксиэтилом, C₁-C₆-диалкиламино, C₁-C₆-диалкиламино-C₁-C₃-алкилом или галогеном фенил, или незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом, C₁-C₆-алкоксиметилом, C₁-C₆- алкоксиэтилом, C₁-C₆-диалкиламино, C₁-C₆-диалкиламино-C₁-C₃-алкилом или галогеном бензил или фенилэтил,
и остальные радикалы обозначают группу вторичных аминов, имеющих от 2 до 18 атомов углерода, R₄₅O- или R₄₅S-, галоген, незамещенный или замещенный циклопентадиенил или мостиковый бисциклопентадиенил или нейтральную связанную группу, где R₄₅ независимо друг от друга обозначают незамещенный или замещенный C₁-C₆- алкоксилом или галогеном C₁-C₁₈-алкил с нормальной или разветвленной цепью, незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆- алкоксилом или галогеном C₅- или C₆-циклоалкил, незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом, C₁-C₆-алкоксиметилом, C₁-C₆-алкоксиэтилом,
C₁-C₆-диалкиламино, C₁-C₆-диалкиламино-C₁-C₃-алкилом или галогеном фенил, или незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом, C₁-C₆-алкоксиметилом, C₁-C₆-алкоксиэтилом, C₁-C₆-диалкиламино, C₁-C₆-диалкиламино- C₁-C₃-алкилом или галогеном бензил или фенилэтил; или в формулах XV, XVa и XVb остальные радикалы независимо друг от друга обозначают группу вторичных аминов, имеющих от 2 до 18 углеродных атомов, R₄₅O- или R₄₅S-, галоген, незамещенный или замещенный циклопентадиенил или мостиковый бисциклопентадиенил или нейтральную связанную группу, где R₄₅ независимо друг от друга обозначают незамещенный или замещенный C₁-C₆-алкоксилом или галогеном C₁-C₁₈-алкил с нормальной или разветвленной цепью, незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом или галогеном C₅- или C₆-циклоалкил, незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом,
C₁-C₆-алкоксиметилом, C₁-C₆- алкоксиэтилом, C₁-C₆-диалкиламино, C₁-C₆-диалкиламино-C₁-C₃-алкилом или галогеном фенил, или незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом, C₁-C₆-алкоксиметилом, C₁-C₆-алкоксиэтилом, C₁-C₆-диалкиламино, C₁-C₆-алкиламино-C₁-C₃-алкилом или галогеном бензил или фенилэтил.In one preferred embodiment of the invention, the metal compounds are particularly consistent with formulas XV, XVa or XVb,

where Me ₁ stands instead of niobium (VI) or tantalum (VI);
Me ₂ stands in place of niobium (V) or tantalum (V);
one of the radicals R ₆₉ —R ₇₄ is the radical —CH ₂ —SiR ₃₈ R ₃₉ R _{40 of the} formula XIV;
at least one of R _{69 to} R ₇₄ is fluoro, chloro or bromo;
R ₃₈ , R _39, and R _{40 are} independently C ₁ -C ₆ alkyl, C ₅ or C ₆ cycloalkyl, or unsubstituted or substituted with C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy phenyl or benzyl;
in formula XV two or at a certain moment two, and in formula XVa two of the remaining radicals R ₆₉ -R ₇₄ together represent = O or = NR ₄₄ , and R ₄₄ represents an unsubstituted or substituted C ₁ -C ₆ alkoxyl C ₁ -C Straight or branched chain ₁₈ alkyl unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxyl or halogen C ₅ or C ₆ cycloalkyl unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxymethyl, C ₁ -C ₆ alkoxyethyl, C ₁ -C ₆ dialkylamino, C ₁ -C ₆ dialkylamino-C ₁ -C ₃ alkyl or phenyl halogen, or unsubstituted or substituted C ₁ -C ₆ -alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ -alkoksimetilom, C ₁ -C ₆ - alkoksietilom, C ₁ -C ₆ dialkylamino, C ₁ -C ₆ dialkylamino-C ₁ -C ₃ alkyl or benzyl or phenylethyl halogen,
and the remaining radicals denote a group of secondary amines having from 2 to 18 carbon atoms, R ₄₅ O— or R ₄₅ S—, halogen, unsubstituted or substituted cyclopentadienyl or a bridged biscyclopentadienyl or a neutral linked group, where R ₄₅ independently represent unsubstituted substituted with C ₁ -C ₆ alkoxyl or halogen C ₁ -C ₁₈ straight or branched chain alkyl, unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxyl or halogen C ₅ - or C ₆ - cycloalkyl unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C _6- alkoxymethyl, C ₁ -C ₆ -alkoxyethyl,
C ₁ -C ₆ dialkylamino, C ₁ -C ₆ dialkylamino-C ₁ -C ₃ -alkyl or halogen phenyl, or unsubstituted or substituted with C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxyl, C ₁ - C ₆ alkoxymethyl, C ₁ -C ₆ alkoxyethyl, C ₁ -C ₆ dialkylamino, C ₁ -C ₆ dialkylamino C ₁ -C ₃ alkyl or halogen benzyl or phenylethyl; or in formulas XV, XVa and XVb, the remaining radicals independently represent a group of secondary amines having from 2 to 18 carbon atoms, R ₄₅ O- or R ₄₅ S-, halogen, unsubstituted or substituted cyclopentadienyl or bridged biscyclopentadienyl or a neutral linked group where R ₄₅ independently from each other is unsubstituted or substituted C ₁ -C ₆ alkoxy or halogen C ₁ -C ₁₈ straight or branched chain alkyl, unsubstituted or substituted by C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or halogen C ₅ or C ₆ cycloalkyl unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxyl,
C ₁ -C ₆ alkoxymethyl, C ₁ -C ₆ alkoxyethyl, C ₁ -C ₆ dialkylamino, C ₁ -C ₆ dialkylamino-C ₁ -C ₃ alkyl or halogen phenyl, or unsubstituted or substituted C ₁ - C ₆ -alkyl, C ₁ -C ₆ alkoxyl, C ₁ -C ₆ alkoxymethyl, C ₁ -C ₆ alkoxyethyl, C ₁ -C ₆ dialkylamino, C ₁ -C ₆ alkylamino-C ₁ -C ₃ -alkyl or halogen benzyl or phenylethyl.

The radicals R ₆₉ to R ₇₄ have the above preferences.

In one of the most preferred embodiments of the invention, the claimed methods are accompanied by the use of metal compounds of the formulas XV, XVa or XVb, where R ₆₉ is a radical of the formula XIV — CH ₂ —SiR ₃₈ R ₃₉ R ₄₀ , and R ₄₀ and R ₇₀ are fluoro, chloro or bromine; and
a) in the formula XV, R ₇₁ and R ₇₂ , as well as R ₇₃ and R _74, respectively, together denote the radical = NR ₄₄ , or R ₇₁ and R ₇₂ together denote the radical = NR ₄₄ , and R ₇₃ and R ₇₄ independently represent unsubstituted or substituted cyclopentadienyl, R ₄₅ —O— or halogen, or
b) in formula XVa and R ₇₂ together denote the radical = NR ₄₄ , and R ₄₄ means unsubstituted or substituted cyclopentadienyl, R ₄₅ -O- or halogen, or in formula XVa R ₇₁ , R ₇₂ and R ₇₃ independently represent unsubstituted or substituted cyclopentadienyl, R ₄₅ —O— or halogen, or
c) in formula XVb, R ₇₁ and R _{72 are} independently unsubstituted or substituted cyclopentadienyl, R ₄₅ —O— or halogen,
moreover, R ₃₈ -R ₄₄ have the above meanings. R ₃₈ , R ₃₉ , R ₄₀ , R ₄₄ and R _{45 are} given the preference indicated above.

При этом Me₁ стоит вместо Mo(XI) или (VI);
Me₂ стоит вместо Nb(V) или Ta(V);
R₇₅ представляет - Si(C₁-C₄-алкил)₃;
Z стоит вместо хлора или брома;
R₆₃ обозначает фенил или фенил, замещенный 1-3 раза C₁-C₄-алкилом или C₁-C₄-алкоксилом,
(а) R₇₃ и R₇₄ в формуле XVI вместе обозначают группу =NR₆₃ или по отдельности, независимо друг от друга фтор, хлор, бром, незамещенный или замещенный фтором C₁-C₄-алкоксил с нормальной или разветвленной цепью, незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом фенилоксил или незамещенный или замещенный C₁-C₄-алкилом циклопентадиенил,
б) R₇₁, R₇₂, R₇₃ и R₇₄ в формуле XVIa независимо друг от друга обозначают фтор, хлор, бром, незамещенный или замещенный фтором C₁-C₄-алкоксил с нормальной или особенно разветвленной цепью, незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом фенилоксил или незамещенный или замещенный C₁-C₄-алкилом циклопентадиенил;
(в) R₇₃ в формуле XVIб представляет фтор, хлор, бром, незамещенный или замещенный фтором C₁-C₄-алкоксил с нормальной или разветвленной цепью, незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом фенилоксил или незамещенный или замещенный C₁-C₄-алкилом циклопентадиенил;
г) R₇₁, R₇₂ и R₇₃ в формуле XVIc независимо друг от друга обозначают фтор, хлор, бром, незамещенный или замещенный фтором C₁-C₄-алкоксил с нормальной или особенно разветвленной цепью, незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом фенилоксил или незамещенный или замещенный C₁-C₄-алкилом циклопентадиенил; и
д) R₇₁ и R₇₂ в формуле XVId независимо друг от друга обозначают фтор, хлор, бром, незамещенный или замещенный фтором C₁-C₄ алкоксил с нормальной или особенно разветвленной цепью, незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом фенилоксил или незамещенный или замещенный C₁-C₄-алкилом циклопентадиенил. Алкоксил представляет собой алкоксил с особенно разветвленной цепью, при необходимости частично или полностью замещенный фтором, например n-пропилоксил, i- и t-бутилоксил, гексафторпропилоксил и нонафторпропилоксил. В отношении радикала фенилоксила говорится в особенности о фенилоксиле, замещенном C₁-C₄-алкилом в положениях 2,6, например 2,6-диметилфенилоксил. Примерами замещенных радикалов циклопентадиенила являются от моно- до пентаметилциклопентадиенила и триметилсилилциклопентадиенил. R₆₃ представляет предпочтительно фенил или фенил, замещенный C₁-C₄-алкилом, особенно фенил, 3,5-диметил-, 2,6-диметил-, 3,5-диэтил- и 2,6-диэтилфенил.Metal compounds of the formulas XVI, XVIa, XVIb, XVIc or XVId have the most preferred use in the claimed method,

Moreover, Me ₁ stands in place of Mo (XI) or (VI);
Me ₂ stands instead of Nb (V) or Ta (V);
R ₇₅ represents - Si (C ₁ -C ₄ alkyl) ₃ ;
Z stands for chlorine or bromine;
R ₆₃ is phenyl or phenyl substituted 1-3 times with C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxyl,
(a) R ₇₃ and R ₇₄ in the formula XVI together denote a group = NR ₆₃ or individually, independently from each other, fluorine, chlorine, bromine, unsubstituted or substituted by fluorine C ₁ -C ₄ alkoxyl with a straight or branched chain, unsubstituted or phenyloxy substituted with C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; or unsubstituted or substituted C ₁ -C ₄ -cyclopentadienyl,
b) R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ in the formula XVIa independently represent fluorine, chlorine, bromine, unsubstituted or substituted by fluorine C ₁ -C ₄ alkoxyl with a normal or especially branched chain, unsubstituted or substituted by C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxyl phenyloxy or unsubstituted or substituted with C ₁ -C ₄ -alkyl cyclopentadienyl;
(c) R ₇₃ in the formula XVIb represents fluorine, chlorine, bromine, unsubstituted or substituted by fluorine C ₁ -C ₄ alkoxyl with a straight or branched chain, unsubstituted or substituted by C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxyl phenyloxy or unsubstituted or substituted with C ₁ -C ₄ alkyl cyclopentadienyl;
d) R ₇₁ , R ₇₂ and R ₇₃ in the formula XVIc are independently fluorine, chlorine, bromine, unsubstituted or substituted by fluorine C ₁ -C ₄ alkoxyl with a normal or especially branched chain, unsubstituted or substituted by C ₁ -C ₄ -alkyl or C ₁ -C ₄ alkoxyl phenyloxy or unsubstituted or substituted with C ₁ -C ₄ alkyl cyclopentadienyl; and
e) R ₇₁ and R ₇₂ in the formula XVId are independently fluorine, chlorine, bromine, unsubstituted or substituted by fluorine C ₁ -C ₄ alkoxyl with a normal or especially branched chain, unsubstituted or substituted by C ₁ -C ₄ -alkyl or C ₁ -C ₄ alkoxy phenyloxy or unsubstituted or substituted with ₁ -C ₄ alkyl cyclopentadienyl. Alkoxyl is a particularly branched alkoxyl, optionally partially or completely substituted by fluorine, for example n-propyloxy, i- and t-butyloxy, hexafluoropropyloxy and nonafluoropropyloxy. With respect to the phenyloxyl radical, it is especially said about phenyloxyl substituted with C ₁ -C ₄ -alkyl at the 2,6 positions, for example 2,6-dimethylphenyloxy. Examples of substituted cyclopentadienyl radicals are mono- to pentamethylcyclopentadienyl and trimethylsilylcyclopentadienyl. R ₆₃ is preferably phenyl or phenyl substituted with C ₁ -C ₄ alkyl, especially phenyl, 3,5-dimethyl-, 2,6-dimethyl-, 3,5-diethyl- and 2,6-diethylphenyl.

The most preferred compounds of the claimed methods are such compounds of formulas XVII, XVIIa, XVIIb, XVIIc and XVIId:
(R ₆₃ -N =) ₂ Me ₁ X _a CH ₂ Si (CH ₃ ) ₃ , (XVII)
(R ₆₃ -N =) R ₇₁ Me ₁ X _a (OR ₆₂ ) CH ₂ Si (CH ₃ ) ₃ , (XVIIa)
R ₇₂ R ₇₃ Me ₂ X _a (OR ₆₂ ) CH ₂ Si (CH ₃ ) ₃ , (XVIIb)
R ₆₃ -N = Me ₂ X _a (OR ₆₂ ) CH ₂ Si (CH ₃ ) ₃ , (XVIIc)
R ₇₁ -TiX _a (OR ₆₂ ) CH ₂ Si (CH ₃ ) ₃ , (XVIId)
where Me ₁ stands in place of Mo (VI) or W (VI);
Me ₂ stands instead of Nb (V) or Ta (V);
X _a stands for fluorine or chlorine;
R ₆₃ is phenyl or phenyl substituted with one to two C ₁ -C ₄ alkyl groups;
R ₆₂ is optionally partially or completely fluorine substituted C ₃ - or C ₄ branched chain alkyl or phenyloxy or phenyloxy substituted with one to three methyl or ethyl groups;
R ₇₂ and R ₇₃ independently from each other are unsubstituted or substituted with one to five methyl groups cyclopentadienyl, X _a or R ₆₂ -; and
R ₇₁ is unsubstituted or substituted with one to five methyl groups cyclopentadienyl, X _a or R ₇₂ -.

Some examples of compounds of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) and tungsten (VI) (in this case, Cp is cyclopentadienyl, and Me is niobium (V) or tantalum (V)) are as follows:
Ti [CH ₂ Si (CH ₃ ) ₃ ] Cl ₃ ,
Ti [CH ₂ Si (CH ₃ ) ₃ ] Br ₃ ,
Cp ₂ Ti [CH ₂ Si (CH ₃ ) ₃ ] Cl,
(CH ₃ ) ₂ Ti [CH ₂ Si (CH ₃ ) ₃ ] Cl,
Cp ₂ Ti [CH ₂ Si (CH ₃ ) ₃ ] Br,
Cp ₂ Ti [CH ₂ Si (CH ₃ ) ₃ ] I,
CpTi [CH ₂ Si (CH ₃ ) ₃ ] [CH ₃ ] Cl,
CpTi [CH ₂ Si (CH ₃ ) ₃ ] Br ₂ ,
[(CH ₃ ) ₂ CHO] ₂ Ti [CH ₂ Si (CH ₃ ) ₃ ] Cl,
[(CF ₃ ) ₂ CHO] ₂ Ti [CH ₂ Si (CH ₃ ) ₃ Cl,
[(CF ₃ ) ₂ CHO] CpTi [CH ₂ Si (CH ₃ ) ₃ ] Cl,
[(CH ₃ ) ₂ CHO] CpTi [CH ₂ Si (CH ₃ ) ₃ ] Cl,
(C ₆ H ₅ O) CpTi [CH ₂ Si (CH ₃ ) ₃ ] Cl,
(2,6-Dimethyl-C ₆ H ₅ O) CpTi [CH ₂ Si (CH ₃ ) ₃ ] Cl,
(2,6-dimethyl-C ₆ H ₅ O) ₂ Ti [CH ₂ Si (CH ₃ ) ₃ ] Cl,
(2,6-Dimethyl-C ₆ H ₅ O) -Ti [CH ₂ Si (CH ₃ ) ₃ ] ₂ Br,
[(CH ₃ ) ₃ CO] CpTi [CH ₂ Si (CH ₃ ) ₃ ] Cl,
[(CF ₃ ) ₂ (CH ₃ ) CO] CpTi [CH ₂ Si (CH ₃ ) ₃ ] Cl,
Me (= NC ₆ H ₅ ) [OCH (CH ₃ ) ₂ ] [(CH ₂ Si (CH ₃ ) ₃ ] Cl,
Cp ₂ Me [(CH ₂ Si (CH ₃ ) ₃ ] Cl ₂ ,
Me (= NC ₆ H ₅ ) [OCH (CF ₃ ) ₂ ] [(CH ₂ Si (CH ₃ ) ₃ ] Cl,
Me (= N-2,6-diisopropylC ₆ H ₃ ) [(CH ₂ Si (CH ₃ ) ₃ ] Cl ₂ ,
Me (-N-2,6-diisopropylC ₆ H ₃ ) [(CH ₃ ) ₂ CHO] [(CH ₂ Si (CH ₃ ) ₃ ] Cl,
Me (= N-2,6-dimethylC ₆ H ₃ ) (2,6-dimethyl-C ₆ -H ₅ O) [CH ₂ Si (CH ₃ ) ₃ ] Cl,
Me (= N-2,6-dimethylC ₆ H ₃ ) ((CF ₃ ) CHO) [CH ₂ Si (CH ₃ ) ₃ Cl,
(= N-2,6-dimethylC ₆ H ₃ ) CpMe [(CH ₂ Si (CH ₃ ) ₃ ] Cl,
(C ₆ H ₅ O) ₂ CpMe [(CH ₂ Si (CH ₃ ) ₃ ] Cl,
(= N-3,5-dimethyl C ₆ H ₃ ) Me [2,6-dimethyl C ₆ H ₃ O)] [(CH ₂ Si (CH ₃ ) ₃ ] Cl,
CpMe [OCH (CH ₃ ) ₂ ] ₂ [(CH ₂ Si (CH ₃ ) ₃ Br,
CpMe [OCH (CH ₃ ) ₂ ] ₂ [(CH ₂ Si (CH ₃ ) ₃ ] Cl,
CpMe [OCH (CF ₃ ) ₂ ] ₂ [(CH ₂ Si (CH ₃ ) ₃ Cl,
CP ₂ Me (methyl) [(CH ₂ Si (CH ₃ ) ₃ ] Cl,
Cp ₂ Me [OCH (CH ₃ ) ₂ ] [(CH ₂ Si (CH ₃ ) ₃ ] Cl,
[OCH (CH ₃ ) ₂ ] ₂ Me [CH ₂ Si (CH ₃ ) ₃ ] Cl ₂ ,
Me (2,6-dimethylphenyloxy) (CH ₃ O) ₂ [(CH ₂ Si (CH ₃ ) ₃ Cl,
Me [CH ₂ Si (CH ₃ ) ₃ ] [OCH (CH ₃ )] (CF ₃ O) ₂ Cl,
W (= NC ₆ H ₅ ) [(OC (CH ₃ ) ₃ ] [CH ₂ -Si- (CH ₃ ) ₃ ] Cl ₂ ,
(2,6-diisopropylphenyloxy) ₂ Me [CH ₂ Si (CH ₃ ) ₃ ] Cl ₂ ,
CpMe [OC (CH ₃ ) ₃ ] [(CH ₂ Si (CH ₃ ) ₃ Cl,
CpMe [OC (CH ₃ ) (CF ₃ ) ₂ ] ₂ [(CH ₂ Si (CH ₃ ) ₃ Cl,
Mo ₂ [(CH ₂ -Si (CH ₃ ) ₃ ) (OCH ₂ C (CH ₃ ) ₃ Cl] ₂ ,
Mo (= N-2,6-diisopropylC ₆ H ₃ ) ₂ [CH ₂ - Si (CH ₃ ) ₃ ] Cl,
W (= NC ₆ -H ₅ ) [(OC (CH ₃ ) ₃ ] ₂ [CH ₂ -Si (CH ₃ ) ₃ Cl,
Mo (= NC ₆ H ₅ ) ₂ [CH ₂ -Si (CH ₃ ) ₃ ] Cl,
Mo (= N-2,6-diisopropylC ₆ -H ₃ ) [(OCH ₂ C (CH ₃ ) ₃ ] ₂ [CH ₂ -Si (CH ₃ ) ₃ Cl.

 The compounds of titanium, niobium, tantalum, molybdenum and tungsten used according to the invention are known and are obtained by known and similar methods from metal halide-substituted compounds suitably substituted by Grignard reactions (Schrock, RR. Murdzeck, JS, Basan, GC, Robbins, J ., Di Mare, M., O'Regan, M., J. Am. Chem. Soc. 112: 3875-86 (1990).

 4. Other suitable photoactive one-component catalysts are niobium (V) or tantalum (V) compounds containing at least two methyl groups or two monosubstituted methyl groups bound to a metal, the substituent not containing a hydrogen atom in position α. These compounds are also thermal catalysts.

The compounds of niobium (V) and tantalum (V) used according to the invention contain one metal atom. A metal-bonded methyl group or a monosubstituted methyl group is bonded at least twice, preferably two to five times, and most preferably two or three times. Such a linked group best fits Formula XI
-CH ₂ -R, (XI)
where R has the above meanings and is preferred.

 The remaining valencies of the niobium atom and tantalum are preferably saturated with thermostable neutral ligands, known in large quantities. Their number may also exceed the stoichiometrically possible amount (solvates). The determination of thermal stability has already been given.

 The values, as well as the preference given to neutral ligands, have been described above.

где Me стоит вместо ниобия (V) или тантала (V); по меньшей мере два, предпочтительно 2 или 3 радикала из R₈₂-R₈₆ обозначают радикал -CH₂-R формулы XI, где R имеет вышеприведенные значения и ему отдается предпочтение;
два из оставшихся радикалов R₈₂-R₈₆ вместе обозначают =O или =N-R₄₄, а R₄₄ представляет незамещенный или замещенный C₁-C₆- алкоксилом C₁-C₁₈-алкил с нормальной или разветвленной цепью, незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом или галогеном C₅- или C₆-циклоалкил, незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом, C₁-C₆-алкоксиметилом, C₁-C₆- алкоксиэтилом, C₁-C₆-диалкиламино, C₁-C₆-диалкиламино-C₁-C₃-алкилом или галогеном фенил, или незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом, C₁-C₆-алкоксиметилом, C₁-C₆- алкоксиэтилом, C₁-C₆-диалкиламино, C₁-C₆-диалкиламино-C₁-C₃- алкилом или галогеном бензил или фенилэтил; и/или остальные радикалы R₈₂-R₈₆ независимо друг от друга обозначают группу вторичных аминов, имеющих от 2 до 18 атомов углерода, R₄₅-O-, R₄₅S-, галоген, циклопентадиенил или бисциклопентадиенил с мостиковой связью или нейтральную связанную группу, где R₄₅ независимо друг от друга представляют незамещенный или замещенный C₁-C₆-алкоксилом или галогеном C₁-C₁₈-алкил с нормальной или разветвленной цепью, незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом или галогеном C₅- или C₆-циклоалкил, незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом,
C₁-C₆-алкоксиметилом, C₁-C₆-алкоксиэтилом, C₁-C₆-диалкиламино, C₁-C₆-диалкиламино-C₁-C₃-алкилом или галогеном фенил, или незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом, C₁-C₆-алкоксиметилом, C₁-C₆-алкоксиэтилом, C₁-C₆-диакиламино, C₁-C₆-диалкиламино-C₁-C₃-алкилом или галогеном бензил или фенилэтил.In one of the preferred embodiments of the invention, the compounds of niobium and tantalum correspond in the best way to the formula XVIII

where Me stands in place of niobium (V) or tantalum (V); at least two, preferably 2 or 3 radicals from R ₈₂ —R ₈₆ represent the —CH ₂ —R radical of formula XI, where R has the above meanings and is preferred;
two of the remaining radicals, R ₈₂ -R ₈₆ together, are = O or = NR ₄₄ , and R ₄₄ is unsubstituted or substituted with C ₁ -C ₆ alkoxy of C ₁ -C ₁₈ straight or branched chain alkyl, unsubstituted or substituted with C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxyl or halogen C ₅ - or C ₆ -cycloalkyl unsubstituted or substituted with C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxyl, C ₁ -C ₆ -alkoxymethyl , C ₁ -C ₆ alkoxyethyl, C ₁ -C ₆ dialkylamino, C ₁ -C ₆ dialkylamino-C ₁ -C ₃ alkyl or halogen phenyl, or unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ -alkoksimetilom, C ₁ -C ₆ - al hydroxyethyl, C ₁ -C ₆ dialkylamino, C ₁ -C ₆ dialkylamino-C ₁ -C ₃ - alkyl or halo benzyl, or phenylethyl; and / or the remaining radicals R ₈₂ —R ₈₆ independently represent a group of secondary amines having from 2 to 18 carbon atoms, R ₄₅ —O—, R ₄₅ S—, halogen, cyclopentadienyl or biscyclopentadienyl with a bridged bond or a neutral linked group where R ₄₅ independently from each other are unsubstituted or substituted C ₁ -C ₆ alkoxyl or halogen C ₁ -C ₁₈ straight or branched chain alkyl, unsubstituted or substituted by C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or halogen, C ₅ - or C ₆ -cycloalkyl, unsubstituted or substituted C ₁ -C ₆ -alkyl, C ₁ -C ₆ -al oxyl,
C ₁ -C ₆ alkoxymethyl, C ₁ -C ₆ alkoxyethyl, C ₁ -C ₆ dialkylamino, C ₁ -C ₆ dialkylamino-C ₁ -C ₃ alkyl or halogen phenyl, or unsubstituted or substituted C ₁ - C ₆ -alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ -alkoksimetilom, C ₁ -C ₆ -alkoksietilom, C ₁ -C ₆ -diakilamino, C ₁ -C ₆ dialkylamino-C ₁ -C ₃ -alkyl or halogen benzyl or phenylethyl.

In one of the most preferred embodiments of the invention, niobium and tantalum compounds of the formula XVIII are used, where
a) R ₈₂ —R ₈₆ each represents a radical of the formula XI —CH ₂ —R, or
b) R ₈₂ and R ₈₃ represent one radical of the formula XI —CH ₂ —R, R ₈₄ and R ₈₅ together represent the radical = NR ₄₄ , and R ₈₆ represents unsubstituted or substituted cyclopentadienyl, R ₄₅ —O— or halogen, or
c) R ₈₂ , R ₈₃ and R ₈₄ each represent a radical of the formula XI — CH ₂ —R, and R ₈₅ and R ₈₆ together represent a radical = NR ₄₄ , or R ₈₂ , R ₈₃ , R ₈₄ and R ₈₅ represent a radical of the formula XI —CH ₂ —R, and R ₈₆ is unsubstituted or substituted cyclopentadienyl, R ₄₅ —O— or halogen,
wherein R, R ₄₄ and R ₄₅ are as defined above. R, R ₄₄ and R _{45 are} preferred, as already mentioned.

где Me стоит вместо ниобия (V) или тантала (V),
R_v представляет -C(CH₃)₃, C(CH₃)₂-C₆H₅, -C₆H₅ или -Si(C₁-C₄-алкил)₃, R₆₃ обозначает фенил или фенил, замещенный от 1 до 3 раз C₁-C₄-алкилом или C₁-C₄-алкоксилом,
R₈₄ в формуле IXX представляет группу -CH₂-R или фтор, хлор, бром, незамещенный или замещенный фтором C₁-C₄-алкоксил с нормальной или особенно разветвленной цепью, незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом фенилоксил или незамещенный или замещенный C₁-C₄-алкилом циклопентадиенил;
R₈₂, R₈₃ и R₈₄ в формуле IXXa обозначают независимо друг от друга фтор, хлор, бром, незамещенный или замещенный фтором C₁-C₄-алкоксил с нормальной или особенно разветвленной цепью, незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом фенилоксил или незамещенный или замещенный C₁-C₄-алкилом циклопентадиенил; и
R₈₂ и R₈₃ в формуле IXXb независимо друг от друга обозначают фтор, хлор, бром, незамещенный или замещенный фтором C₁-C₄-алкоксил с нормальной или в особенности разветвленной цепью, незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом фенилоксил или незамещенный или замещенный C₁-C₄-алкилом циклопентадиенил. Алкоксил является наиболее предпочтительно алкоксилом с разветвленной цепью и замещен при необходимости фтором частично или полностью, например i-пропилоксил, i- и t-бутилоксил, гексафторпропилоксил или нонафторпропилоксил.In the best way in the claimed methods are used compounds of niobium and tantalum of the formulas IXX, IXXa or IXXb,

where Me stands instead of niobium (V) or tantalum (V),
R _v is —C (CH ₃ ) ₃ , C (CH ₃ ) ₂ —C ₆ H ₅ , —C ₆ H ₅ or —Si (C ₁ -C ₄ alkyl) ₃ , R ₆₃ is phenyl or substituted from 1 to 3 times C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxyl,
R ₈₄ in the formula IXX represents a —CH ₂ —R group or fluoro, chloro, bromo, unsubstituted or substituted fluorine C ₁ -C ₄ alkoxyl with a straight or especially branched chain, unsubstituted or substituted with C ₁ -C ₄ -alkyl or C ₁ -C ₄ alkoxy phenyloxy or unsubstituted or substituted by C ₁ -C ₄ alkyl cyclopentadienyl;
R ₈₂ , R ₈₃ and R ₈₄ in the formula IXXa are independently fluorine, chlorine, bromine, unsubstituted or substituted fluorine C ₁ -C ₄ alkoxyl with a normal or especially branched chain, unsubstituted or substituted with C ₁ -C ₄ -alkyl or C ₁ -C ₄ alkoxy phenyloxy or unsubstituted or substituted with C ₁ -C ₄ alkyl cyclopentadienyl; and
R ₈₂ and R ₈₃ in formula IXXb are independently fluorine, chlorine, bromine, unsubstituted or substituted by fluorine C ₁ -C ₄ alkoxyl with a straight or especially branched chain, unsubstituted or substituted by C ₁ -C ₄ -alkyl or C ₁ -C ₄ alkoxy phenyloxy or unsubstituted or substituted with ₁ -C ₄ alkyl cyclopentadienyl. Alkoxyl is most preferably branched chain alkoxyl and optionally substituted partially or completely with fluorine, for example i-propyloxy, i- and t-butyloxy, hexafluoropropyloxy or nonafluoropropyloxy.

Some examples of the compounds of niobium (V) and tantalum (V) (wherein Cp is cyclopentadienyl and Me is niobium (V) or tantalum (V)) are as follows:
Me [CH ₂ Si (CH ₃ ) ₃ ] ₅ ,
CpMe [(CH ₂ C (CH ₃ ) ₂ -C ₆ H ₅ )] ₃ ,
Me (= N-2,6-dimethyl-C ₆ H ₃ ) (CH ₃ ) ₃ ,
Me (= NC ₆ H ₅ ) [OC (CH ₃ ) ₃ ] [(CH ₂ Si (CH ₃ ) ₃ ] ₂ ,
Me (= N-2,6-diisopropylC ₆ H ₃ ) [(CH ₂ -C ₆ H ₅ )] ₃ ,
Me (= NC ₆ H ₅ ) [OCCH ₃ (CF ₃ ) ₂ ] [(CH ₂ Si (CH ₃ ) ₃ ] ₂ ,
CpMe [OCCH ₃ (CF ₃ ) ₂ ] ₂ [(CH ₂ -C ₆ H ₅ )] ₂ ,
Me (= N-2,6-diisopropylC ₆ H ₃ ) [(CH ₂ C (CH ₃ ) ₂ -C ₆ H ₅ )] ₂ Cl,
CpMe (CH ₃ ) ₂ [OCH (CH ₃ ) ₂ ],
Me (= N-2,6-demethylC ₆ H ₃ ) [(CH ₂ -C ₆ H ₅ )] ₃ ,
CpMe [OCH (CH ₃ ) ₂ ] ₂ [(CH ₂ Si (CH ₃ ) ₃ ] ₂ ,
CpMe [(CH ₂ -C ₆ H ₅ )] ₃ ,
Me [CH ₂ Si (CH ₃ )] ₃ Cl ₂ ,
Me [CH ₂ Si (CH ₃ ) ₃ ] ₃ [OCH ₂ (CH ₃ ) ₃ ] ₂ ,
CpMe [3,5-dimethylC ₆ H ₃ O)] [(CH ₂ Si (CH ₃ ) ₃ )] ₂ ,
Me (2,6-diisopropylphenyloxy) ₂ (CH ₃ ) ₃ ,
CpMe (CH ₃ ) ₃ ,
Me (2,6-dimethylphenyloxy) ₂ (CH ₃ ) ₃ ,
Me [CH ₂ Si (CH ₃ ) ₃ ] ₃ [OCH (CH ₃ )] ₂ ,
CpMe [OC (CH ₃ ) ₃ ] ₂ [(CH ₂ -C ₆ H ₅ )] ₂ ,
CpMe [(CH ₂ Si (CH ₃ ) ₃ ] ₃ .

 The niobium and tantalum compounds used according to the invention are known or obtained by known and similar methods, if necessary, from substituted compounds containing a metal halide group using Grignard reactions and / or substitution reactions (Schrock. RR, Murdzeck, JS, Basan, GC, Robbins, J. DiMare, M., O'Regan. M., J. Am. Chem. Soc., 112: 3875-3886 (1990).

 5. The following suitable photoactive one-component catalysts are titanium (IV) compounds containing at least two methyl groups or two monosubstituted methyl groups bound to a metal, the substituent not containing a hydrogen atom in position α. These compounds are also thermal catalysts.

The titanium (IV) compounds used according to the invention contain one metal atom. A metal-bonded methyl group or a monosubstituted methyl group is a group bonded at least twice, preferably 2 to 4 times, and most preferably two to three times. Such a linked group preferably corresponds to formula XI
-CH ₂ -R, (XI)
where R has the above meanings and is preferred.

 The remaining valencies of the titanium atom are preferably saturated with thermostable neutral ligands, known in many. The number of neutral bound groups may also exceed the stoichiometrically possible amount (solvates). The determination of thermal stability has already been given.

With respect to neutral linked groups, we are talking mainly about the same or different linked groups consisting of secondary amines having from 2 to 18 carbon atoms, R ₄₅ O-, R ₄₅ S-, halogen, cyclopentadienyl, bridged biscyclopentadienyl, trident single anionic bound groups and neutral linked groups, such as, for example, ethers and amines, where R ₆₂ independently are unsubstituted or substituted C ₁ -C ₆ alkoxyl or halogen C ₁ -C ₁₈ straight or branched chain alkyl, unsubstituted or deputy C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or halogen C ₅ or C ₆ cycloalkyl, unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C _6- alkoxymethyl, C ₁ -C ₆ alkoxyethyl or halogen phenyl, or unsubstituted or substituted with C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkoxymethyl, C ₁ -C ₆ -alkoxyethyl or benzyl or phenylethyl halogen.

The meanings and preferences given to R ₄₅ , secondary amines, halogen as another group attached to a metal atom, or as a substituent, cyclopentadienyl, ethers, nitriles, tertiary amines and phosphines as neutral ligands and trident single anionic ligands were given above. The meanings and preferences for alkyl, alkoxyl or alkoxyl as a substituent in alkoxymethyl or alkoxyethyl have also been described.

где по меньшей мере два, предпочтительно 2 или 3 радикала из R₈₇-R₉₀ обозначают радикал -CH₂-R формулы XI, где R имеет вышеназванные значения и предпочтения, и
остальные радикалы R₈₇-R₉₀ обозначат вторичные амины с углеродными атомами в количестве от 2 до 18, R₄₅O-, R₄₅S-, галоген, циклопентадиенил или бисциклопентадиенил с мостиковой связью или нейтральную связанную группу, где R₄₅ независимо друг от друга представляют незамещенный или замещенный C₁-C₆-алкоксилом или галогеном C₁-C₁₈-алкил с нормальной или разветвленной цепью, незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом или галогеном C₅- или C₆-циклоалкил, незамещенный или замещенный C₁-C₆-алкилом, C₁-C₆-алкоксилом, C₁-C₆-алкоксиметилом, C₁-C₆-алкоксиэтилом, C₁-C₆-диалкиламино, C₁-C₆-диалкиламино-С₁-С₃-алкилом, C₁-C₆-алкоксилом, C₁-C₆-алкоксиметилом, C₁-C₆-алкоксиэтилом, C₁-C₆-диалкиламино, C₁-C₆-диалкиламино-C₁-C₃-алкилом или галогеном бензил или фенилэтил.In one preferred embodiment of the invention, the titanium (IV) compounds are particularly consistent with formula XX

where at least two, preferably 2 or 3 radicals from R ₈₇ -R ₉₀ denote the radical -CH ₂ -R of formula XI, where R has the above meanings and preferences, and
the remaining radicals R ₈₇ -R _{90 will} represent secondary amines with carbon atoms in an amount of from 2 to 18, R ₄₅ O-, R ₄₅ S-, halogen, cyclopentadienyl or biscyclopentadienyl with a bridged bond or a neutral linked group, where R _{45 is} independently from each other are unsubstituted or substituted C ₁ -C ₆ alkoxyl or halogen C ₁ -C ₁₈ straight or branched chain alkyl, unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxyl or C ₅ -halogen or C ₆ cycloalkyl unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxymethyl , C ₁ -C ₆ alkoxyethyl, C ₁ -C ₆ dialkylamino, C ₁ -C ₆ dialkylamino-C ₁ -C ₃ alkyl, C ₁ -C ₆ alkoxyl, C ₁ -C ₆ alkoxymethyl, C ₁ -C ₆ alkoxyethyl, C ₁ -C ₆ dialkylamino, C ₁ -C ₆ dialkylamino-C ₁ -C ₃ alkyl or halogen benzyl or phenylethyl.

In one of the most preferred embodiments of the invention, the claimed methods use titanium (IV) compounds of formula XX, where
a) R ₈₇ -R ₉₀ denote a radical of the formula XI-CH ₂ -R, or
b) R ₈₇ and R ₈₈ represent a radical of the formula XI — CH ₂ —R, and R ₈₉ and R _{90 are} independently unsubstituted or substituted cyclopentadienyl, R ₄₅ —O— or halogen, or
c) R ₈₇ , R ₈₈ and R ₈₉ represent a radical of the formula XI — CH ₂ —R, and R ₉₀ is unsubstituted or substituted cyclopentadienyl, R ₄₅ —O— or halogen,
wherein R and R ₄₅ have the above meanings and preferences.

где R_v представляет водород, -C(CH₃)₃, -C(CH₃)₂-C₆H₅, -C₆H₅ или -Si(C₁-C₄-алкил)₃, и
R₈₇ и R₈₈ независимо друг от друга обозначают фтор, хлор, бром, незамещенный или замещенный фтором C₁-C₄-алкоксил с нормальной или в особенности разветвленной цепью, незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом фенилоксил или незамещенный или замещенный C₁-C₄-алкилом циклопентадиенил. Алкоксил является наиболее предпочтительно алкоксилом с разветвленной цепью и замещен частично или полностью, при необходимости, фтором, например i-пропилоксил, i- и t-бутилоксил, гексафторпропилоксил и нонафторпропилоксил.The greatest preference in the claimed method are compounds of titanium (IV) of the formula XXIa or XXIb,

where R _v represents hydrogen, —C (CH ₃ ) ₃ , —C (CH ₃ ) ₂ —C ₆ H ₅ , —C ₆ H ₅ or —Si (C ₁ -C ₄ alkyl) ₃ , and
R ₈₇ and R ₈₈ independently of one another are fluoro, chloro, bromo, unsubstituted or substituted fluorine C ₁ -C ₄ alkoxyl with a straight or especially branched chain, unsubstituted or substituted with C ₁ -C ₄ -alkyl or C ₁ -C _4- alkoxyl phenyloxy or unsubstituted or substituted with C ₁ -C ₄ -alkyl cyclopentadienyl. Alkoxyl is most preferably a branched chain alkoxyl and is partially or fully substituted, if necessary, with fluorine, for example i-propyloxy, i- and t-butyloxy, hexafluoropropyloxy and nonafluoropropyloxy.

где Y₁ стоит вместо фтора, хлора или брома;
R₃₈, R₃₉ и R₄₀ независимо друг от друга обозначают C₁-C₁₈-алкил, C₅- или C₆-циклоалкил или незамещенный или замещенный C₁-C₆-алкилом или C₁-C₆-алкоксилом фенил или бензил; а
R₈₇ представляет группу -CH₂-SiR₃₈R₃₉R₄₀, фтор, хлор, бром, незамещенный или замещенный фтором C₁-C₄-алкоксил с нормальной или в особенности разветвленной цепью, незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом фенилоксил или незамещенный или замещенный C₁-C₄-алкилом циклопентадиенил, R₃₈, R₃₉ и R₄₀ обозначают предпочтительно C₁-C₄-алкил, фенил или бензил, a R₈₇ представляет предпочтительно хлор, незамещенный или замещенный фтором C₃- или C₄-алкил или незамещенный или замещенный C₁-C₄-алкилом или C₁-C₄-алкоксилом фенил или бензил.In a preferred embodiment of the invention, the titanium (IV) compounds contain one halogen atom, in particular chlorine or bromine bound to titanium, if in the —CH ₂ —R group the radical R is substituted for —SiR ₃₈ R ₃₉ R ₄₀ . Most preferred are compounds of formula XXII,

where Y ₁ stands instead of fluorine, chlorine or bromine;
R ₃₈ , R ₃₉ and R _{40 are} independently C ₁ -C ₁₈ alkyl, C ₅ or C ₆ cycloalkyl or unsubstituted or substituted with C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy phenyl or benzyl; a
R ₈₇ represents a —CH ₂ —SiR ₃₈ R ₃₉ R ₄₀ group, fluoro, chloro, bromo, unsubstituted or substituted fluoro C ₁ -C ₄ alkoxyl with a straight or especially branched chain, unsubstituted or substituted with C ₁ -C ₄ -alkyl or C ₁ -C ₄ alkoxyl phenyloxy or unsubstituted or substituted with C ₁ -C ₄ alkyl cyclopentadienyl, R ₃₈ , R ₃₉ and R ₄₀ are preferably C ₁ -C ₄ alkyl, phenyl or benzyl, and R ₈₇ is preferably chlorine unsubstituted or substituted by fluorine C ₃ - or C ₄ -alkyl or unsubstituted or substituted by C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxyl phenyl or benzyl.

Some examples of titanium (IV) compounds (where Cp is cyclopentadienyl) are:
Ti [CH ₂ Si (CH ₃ ) ₃ ] ₄ ,
Ti [OCH (CF ₃ ) ₂ ] ₂ [(CH ₂ Si (CH ₃ ) ₃ ] ₂ ,
CpTi [(CH ₂ C (CH ₃ ) ₂ -C ₆ H ₅ )] ₂ Cl,
CpTi [(CH ₂ -C ₆ H ₅ )] ₃ ,
TiCl ₂ [CH ₂ Si (CH ₃ ) ₃ )] ₂ ,
[OCH (CF ₃ ) ₂ ] Ti [(CH ₂ -C ₆ H ₅ )] ₃ ,
CpBrTi [(CH ₂ C (CH ₃ ) ₂ —C ₆ H ₅ )] ₂ ,
CpTi [2,6-dimethylC ₆ H ₃ O)] [(CH ₂ Si (CH ₃ ) ₃ )] ₂ ,
Ti [OCH (CH ₃ ) ₂ ] ₂ [(CH ₂ -C ₆ H ₅ )] ₂ ,
ClTi [OCH (CH ₃ ) ₂ ] [(CH ₂ Si (CH ₃ ) ₃ )] ₂ ,
CpTi [OCH (CF ₃ ) ₂ ] [(CH ₂ -C ₆ H ₅ )] ₂ ,
CpTi (methyl) ₃ ,
CpTi (methyl) ₂ [OCH (CH ₃ ) ₂ ],
Ti [CH ₂ Si (CH ₃ ) ₃ ] ₂ ] Br ₂ ,
Ti (2,6-dimethylphenyloxy) ₂ (CH ₃ ) ₂ ,
CpTi (CH ₃ ) ₂ ,
Ti [CH ₂ Si (CH ₃ ) ₃ ] ₃ [OCH (CH ₃ )],
Ti (2,6-diisopropylphenyloxy) ₂ (CH ₃ ) ₂ .

 The titanium (IV) compounds used in accordance with the invention are known or obtained by known and similar methods from compounds containing a metal halide group using Grignard reactions or other known substitution reactions (see Clauss. K., Bestian, H., Justus Liebigs Ann. Chem. 654: 8-19 (1962)).

 6. Other suitable photocatalytically active compounds are ruthenium and osmium compounds containing at least one phosphine group, at least one photolabile linked group and, if necessary, neutral linked groups bonded to a metal atom, with a total of 2 to 5 such groups containing acid anions to equalize the charge. “Total”, as used herein, means the sum of phosphine groups, photolabile linked groups, and neutral linked groups. Neutral linked groups are also designated as non-photolabile linked groups (ligands). In total there are preferably from 2 to 4, most preferably 2 or 3, linked groups.

Osmium compounds are also thermally active catalysts. Ruthenium compounds are also thermal catalysts if the phosphine group does not contain normal chain alkyl or alkoxyl groups, but contains space-filling groups, for example, secondary and tertiary alkyl or alkoxyl groups (i-propyl, i - and t-butyl), or cycloalkyl groups or unsubstituted or 1 to 3 times substituted with a C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy group of a phenyl or phenyloxyl group.

 The phosphine group is preferably tertiary phosphines with carbon atoms in an amount of from 3 to 40, preferably from 3 to 30, and most preferably from 3 to 24.

 The remaining valencies of ruthenium and osmium are preferably saturated with thermostable neutral ligands, known in large quantities. The number of neutral linked groups may also exceed the stoichiometrically possible number (solvates).

In the ruthenium and osmium compounds used according to the invention, monophosphine can be bound to a metal atom from 1 to 3, preferably 2-3 times, and diphosphine once. In ruthenium and osmium catalysts, there are preferably 1 to 2 bound groups. The bound phosphine groups correspond preferably to formulas XXIII and XXIIIa
PR ₉₁ R ₉₂ R ₉₃ , (XXIII)
R ₉₁ R ₉₂ PZ ₁ -PR ₉₁ R ₉₂ , (XXIIIa)
where R ₉₁ , R ₉₂ and R _{93 are} independently hydrogen, C ₁ -C ₂₀ alkyl unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl or C ₁ -C ₆ alkoxy C ₄ -C ₁₂ cycloalkyl or unsubstituted or substituted with C ₁ -C ₆ -alkyl, C ₁ -C ₆ haloalkyl or C ₁ -C ₆ -alkoxyl C ₆ -C ₁₆ -aryl or unsubstituted or substituted with C ₁ -C ₆ -alkyl, C ₁ -C ₆ haloalkyl or C ₁ -C ₆ alkoxyl C ₇ -C ₁₆ aralkyl; the radicals R ₉₁ and R ₉₂ together are unsubstituted or substituted with C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl or C ₁ -C ₆ -alkoxyl tetra- or pentamethylene, or unsubstituted or substituted with C ₁ -C ₆ -alkyl , C ₁ -C ₆ haloalkyl or C ₁ -C ₆ alkoxy and condensed by 1, 2, 2-phenylene, is tetra- or pentamethylene, and R ₉₃ is as defined above; and
Z ₁ is unsubstituted or substituted C ₁ -C ₄ alkoxyl C ₂ -C ₁₂ straight or branched chain alkylene, unsubstituted or substituted with C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxyl 1,2- or 1 , 3-cycloalkylene having from 4 to 8 carbon atoms, or unsubstituted or substituted with C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxyl 1,2- or 1,3-heterocycloalkylene with five or six ring elements and one heteroatom from the group O or N.

In relation to the radicals R ₉₁ , R ₉₂ and R ₉₃ we are talking about preferably the same radicals.

Insofar as R ₉₁ , R ₉₂ and R ₉₃ are substituted, the substituents are preferably C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ alkoxyl. Halogen is preferably chlorine and most preferably fluorine. Examples of preferred substituents are methyl, methoxyl, ethyl, ethoxyl and trifluoromethyl. R ₉₁ , R ₉₂ and R ₉₃ are preferably substituted with one to three substituents. The substituents are preferably in one or both of the ortho and / or meta positions for the carbon atom of the PC bond in phosphine.

R ₉₁ , R ₉₂ and R ₉₃ are alkyl and may have a straight or branched chain and preferably from 1 to 12, most preferably from 1 to 8, and most preferably from 1 to 6 carbon atoms. Examples of alkyl are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, isomers of pentyl, hexyl heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and eicosil. Preferably, it is methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, 1-, 2- or 3-pentyl and 1-, 2-, 3- or 4-hexyl.

If R ₉₁ , R ₉₂ and R ₉₃ are cycloalkyl, this is preferably C ₅ -C ₈ cycloalkyl and most preferably C ₅ or C ₆ cycloalkyl. Some examples are cyclobutyl, cycloheptyl, cyclooctyl and especially cyclopentyl and cyclohexyl. Examples of substituted cycloalkyl are methyl, demethyl, trimethyl, methoxy, dimethoxyl, trimethoxyl, trifluoromethyl, bistrifluoromethyl and tristrifromethylcyclopentyl and cyclohexyl.

If R ₉₁ , R ₉₂ and R ₉₃ are aryl, it is preferably C ₆ C ₁₂ aryl and most preferably phenyl or naphthyl. Examples of substituted aryl are methyl, dimethyl, trimethyl, methoxy, dimethoxyl, trimethoxyl, trifluoromethyl, bistrifluoromethyl and tristrifluoromethylphenyl.

If R ₉₁ , R ₉₂ and R ₉₃ are aralkyl, this is preferably a C ₇ -C ₁₃ aralkyl, the alkyl group in the aralkyl being preferably methylene. The most preferred aralkyl is benzyl. Examples of substituted aralkyl are methyl, dimethyl, trimethyl, methoxy, dimethoxyl, trimethoxyl, trifluoromethyl, bistrifluoromethyl and tristrifluoromethylbenzyl.

Другими подходящими фосфинами являются циклоалифаты, связанные мостиковой связью с =PRa-группой и имеющие от 6 до 8 углеродных атомов кольца, например

где Ra обозначает C₁-C₆-алкил, циклогексил, бензил, незамещенный или замещенный одним или двумя C₁-C₄-алкилами фенил.Examples of optionally substituted or fused tetra- or pentamethylene bound to the P atom are

Other suitable phosphines are cycloaliphates bridged to a = PRa group and having 6 to 8 carbon ring atoms, for example

wherein Ra is C ₁ -C ₆ alkyl, cyclohexyl, benzyl, unsubstituted or substituted with one or two C ₁ -C ₄ alkyl phenyl.

With respect to Z ₁ as a straight or branched chain alkylene, it is preferable to 1,2-alkylene or 1,3-alkylene, which preferably contains from 2 to 6 carbon atoms, for example ethylene, 1,2-propylene or 1,2 butylene.

Examples of Z ₁ as cycloalkylene are 1,2- and 1,3-cyclopentylene and 1,2- or 1,3-cyclohexylene. Examples of Z ₁ as heterocycloalkylene are 1,2- and 1,3-pyrrolidine, 1,2- and 1,3-piperidine, and 1,2- and 1,3-tetrahydrofuran.

In one preferred embodiment of the invention, the phosphine ligands correspond to the formula XXIII, where R ₉₁ , R ₉₂ and R ₉₃ independently represent hydrogen, C ₁ -C ₆ alkyl, unsubstituted or substituted with C ₁ -C ₄ alkyl cyclopentyl or cyclohexyl or unsubstituted or substituted with C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or trifluoromethyl phenyl or unsubstituted or substituted with C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or benzyl trifluoromethyl. The most preferred examples of bound phosphine groups of formula XXIII are (C ₆ H ₅ ) ₃ P, (C ₆ H ₅ CH ₂ ) ₃ P, (C ₅ H ₁₁ ) ₃ P, (CH ₃ ) ₃ P, (C ₂ H ₅ ) ₃ P,
(nC ₃ H ₇ ) ₃ P, (iC ₃ H ₇ ) ₃ P, (nC ₄ H ₉ ) ₃ P, (C ₆ H ₅ ) ₂ HP, (C ₆ H ₅ CH ₂ ) ₂ HP, (C ₅ H ₁₁ ) ₂ HP, (C ₂ H ₅ ) ₂ HP, (nC ₃ H ₇ ) ₂ HP, (iC ₃ H ₇ ) ₂ HP, (nC ₄ H ₉ ) ₂ HP,
(C ₆ H ₅ ) H ₂ P, (nC ₄ H ₉ ) H ₂ P, (C ₆ H ₅ CH ₂ ) H ₂ P, (C ₅ H ₁₁ ) H ₂ P, (CH ₃ ) H ₂ P, (CH ₃ ) ₂ HP, (C ₂ H ₅ ) H ₂ P, (nC ₃ H ₇ ) H ₂ P, (iC ₃ H ₇ ) H ₂ P, PH ₃ (2-methyl-C ₆ H ₄ ) ₃ P, (3-CH ₃ -C ₆ H ₄ ) ₃ P, (4-C ₂ H ₅ -C ₆ H ₄ ) ₃ P, (4-CH ₃ -C ₆ H ₄ ) ₃ P, (2,4 -di-CH ₃ -C ₆ H ₃ ) ₃ P,
(2,6-di-CH ₃ -C ₆ H ₃ ) ₃ P, (2-C ₂ H ₅ -C ₆ H ₄ ) ₃ P, (3-C ₂ H ₅ -C ₆ H ₄ ) ₃ P,
(2-nC ₃ H ₇ -C ₆ H ₄ ) ₃ P, (3-nC ₃ H ₇ -C ₆ H ₄ ) ₃ P, (4-nC ₃ H ₇ -C ₆ H ₄ ) ₃ P,
(2-iC ₃ H ₇ -C ₆ H ₄ ) ₃ P, (3-iC ₃ H ₇ -C ₆ H ₄ ) ₃ P, (3-iC ₃ H ₇ -C ₆ H ₄ ) ₃ P,
(2-nC ₄ H ₉ -C ₆ H ₄ ) ₃ P, (3-nC ₄ H ₉ -C ₆ H ₄ ) ₃ P, (4-nC ₄ H ₉ -C ₆ H ₄ ) ₃ P,
(2-iC ₄ H ₉ -C ₆ H ₄ ) ₃ P, (3-iC ₄ H ₉ -C ₆ H ₄ ) ₃ P, (4-iC ₄ H ₉ -C ₆ H ₄ ) ₃ P,
(2-tC ₄ H ₉ -C ₆ H ₄ ) ₃ P, (3-tC ₄ H ₉ -C ₆ H ₄ ) ₃ P, (4-tC ₄ H ₉ -C ₆ H ₄ ) ₃ P,
(2-CH ₃ -6-tC ₄ H ₉ -C ₆ H ₃ ) ₃ P, (3-CH ₃ -6-tC ₄ H ₉ -C ₆ H ₃ ) ₃ P, (4-CH ₃ -6- tC ₄ H ₉ -C ₆ H ₃ ) ₃ P,
(2,6-di-tC ₄ H ₉ -C ₆ H ₃ ) ₃ P, (2,3-di-tC ₄ H ₉ -C ₆ H ₃ ) ₃ P and (2,4-di-tC ₄ H ₉ -C ₆ H ₃ ) ₃ P. For the ruthenium and osmium compounds used according to the invention, organic or inorganic compounds, atoms or ions condensed in a metal center are referred to as linked groups.

 The above values and preferences for photolabile linked groups and non-photolabile linked groups, also designated as intensely coordinating ligands.

 In one preferred embodiment of the invention, the ruthenium and osmium catalysts used according to the invention contain only photolabile ligands, phosphine groups and anions for charge equalization. Most preferred are catalysts having, as photolabile linked groups, arene groups, a tertiary phosphine group, and monovalent or divalent anions for charge equalization.

Suitable anions of inorganic and organic acids are, for example, hydride (H ^⊖ ), halide (e.g. F ^⊖ , Cl ^⊖ , Br ^⊖ and l ^⊖ ), an oxygen acid anion, and BF $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{4}}$ , PF $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{6}}$ , Sbf $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{6}}$ or asf $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{6}}$ . It should be noted that the aforementioned cyclopentadienyl is a ligand and anion.

Other suitable anions are C ₁ -C ₁₂ -, preferably C ₁ -C ₆ and most preferably C ₁ -C ₄ alcoholates, in particular branched chains, for example of the formula R _x R _y R _z CO ^⊖ , where R _x is hydrogen or C ₁ -C ₁₀ alkyl, R _y is C ₁ -C ₁₀ alkyl, and R _z is C ₁ -C ₁₀ alkyl or phenyl, and the total number of carbon atoms R _x , R _y and R _z is 11 As examples, i-propyloxy and t-butyloxy are particularly suitable.

-цепью, например формулы R_xR_yR_zC-, или представляет незамещенный или замещенный одним-тремя C₁-C₄-алкилами или C₁-C₄-алкоксилами фенил или бензил. Некоторыми примерами являются i-пропил-, i- и t-бутил-, фенил-, бензил-, 2-метил-, 2,6-диметил-, 2-i-пропил-, 2-i-пропил-6-метил-, 2-t-бутил-, 2,6-ди-t-бутил- и 2-метил-6- t-бутилфенилацетилид.Other suitable anions are C ₃ -C ₁₈ -, preferably C ₅ -C ₁₄ and most preferably C ₅ -C ₁₂ acetylides, which may correspond to the formula R _w -C≡C ^⊖ , where R _w is C ₁ -C ₁₆ - branched alkyl, preferably C ₃ -C ₁₂ alkyl

a chain, for example of the formula R _x R _y R _z C—, or is unsubstituted or substituted by one to three C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxyl phenyl or benzyl. Some examples are i-propyl-, i- and t-butyl-, phenyl-, benzyl-, 2-methyl-, 2,6-dimethyl-, 2-i-propyl-, 2-i-propyl-6-methyl -, 2-t-butyl-, 2,6-di-t-butyl- and 2-methyl-6-t-butylphenylacetylide.

 The values and preferences for anions of oxygen acids were given above.

а также циклопентадиенил (Cp^⊖).
Количество нефотолабильных связанных групп зависит от количества фосфиновых групп, размеров нефотолабильных связанных групп и количества фотолабильных связанных групп.Most preferred are

as well as cyclopentadienyl (Cp ^⊖ ).
The number of non-photolabile bound groups depends on the number of phosphine groups, sizes of non-photolabile bound groups and the number of photolabile bound groups.

In one of the preferred embodiments of the invention, the compounds of ruthenium and osmium correspond best to one of the formulas XXIV-XXIVf
R ₉₇ L ₁ Me ²⁺ (Z ^n- ) _{2 / n} , (XXIV)
R ₉₇ L ₂ L ₃ Me ²⁺ (Z ^n- ) _{2 / n} , (XXIVa)
(R ₉₇ ) ₂ L ₂ Me ²⁺ (Z ^n- ) _{2 / n} , (XXIVb)
(R ₉₇ ) ₃ L ₂ Me ²⁺ (Z ^n- ) _{2 / n} , (XXIVc)
R ₉₇ L ₁ L ₂ Me ²⁺ (Z ^n- ) _{2 / n} , (XXIVd)
R ₉₇ L ₂ L ₂ Me ²⁺ (Z ^n- ) _{2 / n} , (XXIVe)
R ₉₇ L ₁ L ₃ Me ²⁺ (Z ^n- ) _{2 / n} , (XXIVf)
where R ₉₇ is a tertiary phosphine of the formula XXIII or XXIIIa;
Me stands instead of ruthenium or osmium;
n stands for integers 1, 2 or 3;
Z is an anion of an inorganic or organic acid;
(a) L ₁ is an arene or heteroarene linked group;
(b) L ₂ represents a monovalent photolabile linked group other than L ₁ , and
(c) L ₃ is a monovalent non-photolabile linked group.

R ₉₇ , L ₈ , L ₉ and L ₁₀ have the preferences indicated above for the individual values.

In formulas XXIV-XXIVf, n is preferably instead of 1 or 2 and most preferably instead of 1. R ₉₇ has the preferences indicated for the phosphine groups of formula XXIII, in particular tertiary phosphines.

и в формуле XXVf обозначает H^⊖, циклопентадиенил,

R₉₄, R₉₅ и R₉₆ независимо друг от друга представляют C₁-C₆-алкил, незамещенный или замещенный одним-тремя C₁-C₄-алкилами циклопентил или циклогексил или циклопентилоксил или циклогексилоксил, или незамещенный или замещенный одним-тремя C₁-C₄-алкилами фенил или бензил или фенилоксил или бензилоксил;
L₈ обозначает незамещенный или замещенный одним-тремя C₁-C₄-алкилами, C₁-C₄-алкоксилом, -OH, -F или Cl C₆-C₁₆-арен или C₅-C₁₆-гетероарен;
L₉ обозначает C₁-C₆-алкил-CN, бензонитрил или бензилнитрил, а
L₁₀ обозначает H₂O или C₁-C₆-алканол.In the best way in the claimed method uses compounds of ruthenium and osmium of one of the formulas XXV-XXVf,
(R ₉₄ R ₉₅ R ₉₆ P) L ₈ Me ²⁺ (Z ^1- ) ₂ , (XXV)
(R ₉₄ R ₉₅ R ₉₆ P) ₂ L ₉ Me ²⁺ (Z ^1- ) ₂ , (XXVa)
(R ₉₄ R ₉₅ R ₉₆ P) L ₉ L ₁₀ Me ²⁺ (Z ^1- ) ₂ , (XXVb)
(R ₉₄ R ₉₅ R ₉₆ P) ₃ L ₉ Me ²⁺ (Z ^1- ) ₂ , (XXVc)
(R ₉₄ R ₉₅ R ₉₆ P) L ₉ L ₉ Me ²⁺ (Z ^1- ) ₂ , (XXVd)
(R ₉₄ R ₉₅ R ₉₆ P) L ₈ L ₁₀ Me ²⁺ (Z ^1- ) ₂ , (XXVe)
(R ₉₄ R ₉₅ R ₉₆ P) L ₈ (L ₉ ) _m Me ²⁺ (Z ^1- ) ₂ , (XXVf)
where Me stands instead of ruthenium and osmium;
Z in the formulas XXV-XXVe means H ^⊖ , cyclopentadienyl,

and in the formula XXVf is H ^⊖ , cyclopentadienyl,

R ₉₄ , R ₉₅ and R ₉₆ independently represent C ₁ -C ₆ alkyl unsubstituted or substituted with one to three C ₁ -C ₄ alkyl cyclopentyl or cyclohexyl or cyclopentyloxy or cyclohexyloxy, or unsubstituted or substituted with one to three C ₁ -C ₄ alkyl phenyl or benzyl or phenyloxy or benzyloxy;
L ₈ is unsubstituted or substituted with one to three C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, -OH, -F or Cl C ₆ -C ₁₆ arene or C ₅ -C ₁₆ heteroarene;
L ₉ is C ₁ -C ₆ -alkyl-CN, benzonitrile or benzyl nitrile, and
L ₁₀ is H ₂ O or C ₁ -C ₆ alkanol.

Of the arenes and heteroarenes, benzene, toluene, xylene, trimethylbenzene, naphthalene, biphenyl, anthracene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene, fluororantren, furan, thiophene, pyrrole, pyridine, γ-pyran, γ-thiopyran, pyrimidine are preferred , indole, coumaron, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline, acridine, chloromene, phenazine, phenoxazine, triazine, phenotazine, phenotrazine, triazine, phenotazine, phenotazine, phenazine, phenotazine, phenotazine, phenotazine, phenotazine, phenotrazine. The most preferred arenes and heteroarenes are benzene, naphthalene, cumene, thiophene and benzthiophene. Benzene and benzene substituted with C ₁ -C ₄ alkyl, such as toluene, xylene, isopropylbenzene, tertiary butylbenzene or cumene, are best suited for arenes, and thiophene is the best heteroarene.

 If the production of ruthenium and osmium catalysts occurs in solvents with the possibility of coordination near a metal atom, such as alkanols, solvation cationic complexes of ruthenium or osmium can be formed, which according to the invention are given as part of the application.

Some examples of ruthenium and osmium compounds used according to the invention (in this case, Tos is tosylate) are:
(C ₆ H ₁₁ ) ₂ HPRu (p-cumene) Cl ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (p-cumene) Cl ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (p-cumene) (tos) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (p-cumene) Br ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (p-cumene) ClF,
(C ₆ H ₁₁ ) ₃ PRu (C ₆ H ₆ ) (tos) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (CH ₃ -C ₆ H ₅ ) (tos) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (iC ₃ H ₇ ) -C ₆ H ₅ ) (tos) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (chrysen) (tos) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (biphenyl) (tos) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (anthracene) (tos) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (C ₁₀ H ₈ ) (tos) ₂ ,
(iC ₃ H ₇ ) ₃ PRu (p-cumene) Cl ₂ ,
(CH ₃ ) ₃ PRu (p-cumene) Cl ₂ ,
(nC ₄ H ₉ ) ₃ PRu (p-cumene) Cl ₂ ,
[(C ₆ H ₁₁ ) ₃ P] ₂ Ru (CH ₃ -CN) (tos) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (CH ₃ -CN) (C ₂ H ₅ ) -OH) (tos) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (p-cumene) (CH ₃ -CN) ₂ (PF ₆ ) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (p-cumene) (CH ₃ -CN) ₂ (tos) ₂ ,
(nC ₄ H ₉ ) ₃ PRu (p-cumene) (CH ₃ -CN) ₂ (tos) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (CH ₃ CN) Cl ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (CH ₃ -CN) ₂ Cl ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (p-cumene) (C ₂ H ₅ OH) (BF ₄ ) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (p-cumene) (C ₂ H ₅ OH) ₂ (BF ₄ ) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (p-cumene) (C ₂ H ₅ OH) ₂ - (PF ₆ ) ₂ ,
(C ₆ H ₁₁ ) ₃ PRu (C ₆ H ₆ OH) (C ₂ H ₅ OH) ₂ (tos) ₂ ,
(C ₆ H ₁₁ ) ₃ POs (p-cumene) Cl ₂ ,
(iC ₃ H ₇ ) ₃ POs (p-cumene) Cl ₂ ,
(CH ₃ ) ₃ POs (p-cumene) Cl ₂ ,
(C ₆ H ₅ ) ₃ POs (p-cumene) Cl ₂ ,
RuCl ₂ (p-cumene) [(C ₆ H ₁₁ ) ₂ PCH ₂ CH ₂ P (C ₆ H ₁₁ ) ₂ ].

The ruthenium and osmium compounds used in accordance with the invention are known and can be obtained by known and similar methods from compounds containing metal halides (for example MeX ₃ or [MeArenX ₂ ] ₂ ) by reaction with phosphines and formers of bound groups.

7. Other suitable one-component catalysts are divalent cationic ruthenium or osmium compounds with one metal atom, to which 1-3 tertiary phosphine ligands are attached with substituents (in the case of ruthenium compounds) that need space, if necessary, non-labile neutral ligands and anions for equalization charges, with the proviso that in the (trisphenylphosphine) ruthenium dihalide or halide, the phenyl groups are substituted with C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ haloalkyl or C ₁ -C ₁₈ alkoxy.

 The ruthenium and osmium compounds preferably contain 2 or 3 tertiary phosphine groups. Under the groups of phosphines in the framework of this invention refers to tertiary phosphines. The number of additional non-photolabile bound groups is composed, firstly, of the number of bound phosphine groups and, secondly, of the valency of neutral bound groups. Preference is given to neutral groups with one bond.

 In one preferred embodiment of the invention, the divalent cationic compounds of ruthenium and osmium used according to the invention contain 3 phosphine groups and two monovalent anions to equalize the charges; or 3 phosphine groups, two neutral groups with one bond or one non-photolabile neutral group with two bonds and two monovalent anions to equalize the charges; or 2 phosphine groups, one non-photolabile neutral group with one anion and additionally with one bond and one monovalent anion to equalize charges.

 Above, the meanings and preferences for non-labile linked groups (also named as intensely coordinating ligands) were given.

 The substituents for which space is necessary are called within the framework of the invention those which block the atoms of ruthenium and osmium in space. Surprisingly, it was found that normal-chain alkyl groups as substituents in phosphine linked groups reveal ruthenium compounds without the slightest thermal activity for the metathesis polymerization of hindered cycloolefins. It has also been observed that when using the osmium compounds of the normal-chain alkyl group as substituents in phosphine linked groups, unexpectedly exceptional exceptional thermocatalytic activity was observed for the polymerization of hindered cycloolefins; for osmium compounds, however, phosphine ligands with substituents that require space are also preferably used. In addition, it was found that the spatial screening of triphenylphosphine linked groups in dihalohydrides and hydride halides is insufficient, and such catalysts have only moderate catalytic activity for the metathesis polymerization of hindered cycloolefins. Catalytic activity can be brought to an extremely high level if the tertiary phosphine groups contain phenyl substituted with alkyl or alkoxyl groups.

 The above values were given and indicated the preference of phosphine-linked groups.

With respect to R ₉₁ , R ₉₂ and R ₉₃ as alkyl, it is most preferably a branched-chain alkyl, for example, the formula —CR _b P _c P _d where R is hydrogen or C ₁ -C ₁₂ alkyl, R _c is C ₁ -C ₁₂ alkyl, and R _d is C ₁ -C ₁₂ alkyl or unsubstituted or substituted with C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy phenyl, and the number of carbon atoms in the -CR radical _b P _c P _d is from 3 to 18.

In the compounds used, osmium R ₉₁ , R ₉₂ and R ₉₃ can also be a normal chain alkyl having from 1 to 18, preferably from 1 to 12, most preferably from 1 to 8, and preferably from 1 to 6 carbon atoms, for example methyl , ethyl, n-butyl, n-propyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.

In one preferred embodiment of the invention, the phosphine ligands correspond to formula XXIII, where R ₉₁ , R ₉₂ and R ₉₃ independently represent branched C ₃ -C ₈ alkyl, unsubstituted or substituted with C ₁ -C ₄ alkyl cyclopentyl or cyclohexyl, or unsubstituted or substituted with C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or phenyl trifluoromethyl. The best examples of phosphine linked groups of formula XXIII are:
(C ₆ H ₅ ) ₃ P, (C ₅ H ₉ ) ₃ P, (C ₆ H ₁₁ ) ₃ P,
(iC ₃ H ₇ ) ₃ P, (tC ₄ H ₉ ) ₃ P,
(iC ₄ H ₉ ) ₃ P, [C ₂ H ₅ -CH (CH ₃ )] ₃ P, [C ₂ H ₅ -C (CH ₃ ) ₂ ] ₃ P,
(2-methylphenyl) ₃ P,
(2,3-dimethylphenyl) ₃ P,
(2,4-dimethylphenyl) ₃ P,
(2,6-dimethylphenyl) ₃ P,
(2-methyl-4-i-propylphenyl) ₃ P,
(2-methyl-3-i-propylphenyl) ₃ P,
(2-methyl-5-i-propylphenyl) ₃ P,
(2,4-di-t-butylphenyl) ₃ P,
(2-methyl-6-i-propylphenyl) ₃ P,
(2-methyl-3-t-butylphenyl) ₃ P,
(2,5-di-t-butylphenyl) ₃ P,
(2-methyl-4-t-butylphenyl) ₃ P,
(2-methyl-5-i-butylphenyl) ₃ P,
(2,3-di-t-butylphenyl) ₃ P,
(2,6-di-t-butylphenyl) ₃ P.

 Examples and preferences for suitable anions have been given above.

In one of the preferred embodiments of the invention, the compounds of ruthenium and osmium correspond in the best way to the formulas XXVI, XXVIa, XXVIb, XXVIc or XXVId
Me ^2⊕ (L ₁₁ ) ₂ (L ₁₂ ) (Y $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{1}}$ ) ₂ (XXVI)
Me ^2⊕ (L ₁₁ ) ₃ (Y $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{1}}$ ) ₂ (XXVIa)
Me ^2⊕ (L ₁₁ ) ₂ L ₁₃ (Y $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{1}}$ ) (XXVIb)
Me ^2⊕ (L ₁₁ ) ₃ L ₁₄ (Y $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{1}}$ ) ₂ (XXVIc)
Me ^2⊕ L ₁ (L ₂ ) ₃ (Y $\genfrac{}{}{0ex}{}{\text{⊖}}{\text{1}}$ ) ₂ (XXVId)
where Me stands in place of ruthenium or osmium;
Y ₁ denotes the anion of a monobasic acid;
L ₁₁ represents a phosphine of the formula XXIII or XXIIIa;
L ₁₂ is a neutral linked group;
L ₁₃ represents unsubstituted or substituted with C ₁ -C ₄ alkyl cyclopentadienyl; a
L ₁₄ stands in place of CO.

The individual values of L ₁₁ , L ₁₂ , L ₁₃ and Y ₁ are given the preferences mentioned above.

In one of the most preferred embodiments of the invention, L ₁₂ in the formula XXVI stands for C ₁ -C ₄ alkanol, Y ₁ in the formula XXVIb stands for chlorine or bromine, Y ₁ in the formula XXVIc stands for hydrogen, and L ₁₁ in the formulas XXVI- XXVIc stands in place of tri-i-propylphosphine, tricyclohexylphosphine, triphenylphosphine or triphenylphosphine substituted in the phenyl groups with one to three C ₁ -C ₄ alkyls.

The ruthenium and osmium compounds used in accordance with the invention are known or can be obtained by known and similar methods from compounds containing metal halides, for example MeX ₃ , [Me (diolefin) X ₂ ] ₂ or [MeArenX ₂ ] ₂ , by reaction with phosphines and shapers of related groups.

где Q₁ и Q₂ имеют значения и предпочтения, указанные для радикалов формулы II.The claimed composition may additionally contain other, having an open chain hindered cyclic and / or hindered polycyclic condensed olefins, forming metathesis polymerizates, and these olefins preferably also contain other double bonds and contribute to the formation of network polymerizates. With respect to cyclic olefins, one can speak of monocyclic or polycyclic fused ring systems, for example having from 2 to 4 rings, which are unsubstituted or substituted and may contain heteroatoms, for example O, S, N or Si, in one or more rings and / or fused aromatic or heteroaromatic rings, for example o-phenylene, o-naphthylene, o-pyridinyl or o-pyrimidinyl. Some cyclic rings may contain from 3 to 16, preferably from 3 to 12, and most preferably from 3 to 8 ring elements. Cyclic olefins may also contain other non-aromatic double bonds, depending on the size of the ring, preferably from 2 to 4 such additional double bonds. With respect to ring substituents, we are talking about such substituents that are inert, that is, do not violate the chemical stability of one-component catalysts. Such olefins and cycloolefins are known in large quantities and can be obtained in a simple way by conducting Diels-Alder reactions with cyclodienes and cycloolefins or polycyclic or polycyclic condensed olefins. Such cycloolefins may correspond, for example, to formula IIa

where Q ₁ and Q ₂ have the meanings and preferences indicated for the radicals of formula II.

 Some preferred examples of compounds of formula IIa are norbornene and norbornene derivatives. Of particular note are (25) - (69), presented at the end of the description.

 The claimed composition may also contain other non-volatile open chain comonomers, forming copolymers with hindered cycloolefins. When used together, for example, dienes, crosslinked polymerizates can form. Some examples of such comonomers are compounds unsaturated with mono- or diolefins, such as olefins and dienes from the group of pentene, hexene, heptene, octene, decene, dodecylene, acrylic and methacrylic acids, their esters and amides, vinyl ether, styrene, butadiene , isoprene and chlorobutadiene.

 Other polymerizable olefins are present in the claimed composition, for example, in an amount up to 80 wt.%, Preferably from 0.1 to 80, most preferably from 0.3 to 60, and preferably from 5 to 40 wt.% In terms of the total number of compounds of formula I and other olefins capable of polymerization.

 The catalytic amount within the framework of the inventive invention is preferably from 0.001 to 20 mol%, more preferably from 0.01 to 15, most preferably from 0.01 to 10, and most preferably from 0.01 to 5 mol%, based on the amount of monomer . Due to the high photocatalytic activity of ruthenium and osmium catalysts containing phosphine groups, amounts from 0.001 to 2% by weight are most preferred in this case.

 The claimed composition may contain solvents, especially if it is used to obtain coatings.

 Inert solvents suitable for these purposes are, for example, polar protic and nonprotonic solvents, which can be used either alone or in combination of at least two solvents. Examples are ether (dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl or ethylene glycol dimethyl ether, ethylene glycol monoethyl or ethylene glycol diethyl ether, diethylene glycol diethyl ether 1,2-methylene chloride, 1,2-methylene chloride, 1,2-methylene ether, trichloroethane, 1,1,2,2-tetrachloroethane), carboxylic acid ester and lactones (ethyl acetate, methyl propionic acid, ethyl benzoic acid, 2-methoxy thyl acetate, γ-butyrolactone, δ-valerolactone, pivalolactone), carboxylic acid and lactam amides (N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, tetramethylurea, hexamethylphosphoric triamide, γ-butyl , N-methylpyrrolidone, N-acetylpyrrolidone, N-methylcaptolactam), sulfoxides (dimethyl sulfoxide), sulfones dimethyl sulfone, diethyl sulfone, trimethylene sulfone, tetramethylene sulfone), tertiary amines (N-methyl piperidine, N-methyl morpholines, for example, and) petroleum ether pentane, hexane, cyclohexane, methylcyclohexane, benzene or substituted benzenes (chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, nitrobenzene, toluene, xylene) and nitriles (acetonitrile, propionitrile, benzonitrile, phenylacetonitrile).

 The best solvents are polar non-protic and non-polar.

 The choice of solvents depends mainly on the properties of single-component catalysts that should not be deactivated when using solvents. Ruthenium and osmium catalysts can be used together with polar solvents, such as, for example, water or alkanols. Such catalysts are also not susceptible to air, oxygen and humidity, and the corresponding compositions capable of forming a polymer network can be processed without special precautions. When using other single-component catalysts, it is recommended that oxygen and humidity be excluded. The compositions are stable during storage, and due to their sensitivity to light, storage in a dark place is recommended.

. Другими средствами, повышающими вязкость, являются полибутадиен, полиизопрен или полихлорбутадиен, а также сополимеры бутадиена, изопрена и хлоропрена с олефинами. Вещества, повышающие вязкость, могут присутствовать в количестве от 0,1 до 50 вес.%, предпочтительно от 1 до 30 и наиболее предпочтительно от 1 до 20 вес.% в пересчете на количество состава. При использовании наполнителей целесообразно сохранять для полимеризации оптическую прозрачность или вести процесс полимеризации в тонких слоях.The claimed composition may contain excipients. Known excipients are antistatic agents, antioxidants, antioxidants that protect against the effects of light or sunlight, softeners, dyes, pigments, fillers, active fillers, processing aids for improving plastics processing, adhesion improvers, viscosity enhancers and excipients for improving removal products from (press) form. Fillers can be present in unexpectedly large quantities without adversely affecting the polymerization process, for example in an amount of up to 70 wt.%, Preferably from 1 to 70, more preferably from 5 to 60, most preferably from 10 to 50, and best of all from 10 to 40 wt.% in terms of the amount of composition. Fillers and active fillers used to improve optical, physical, mechanical and electrical properties are known in large quantities. Some examples are glass and quartz in the form of powders, grains and fibers, oxides of metals and semimetals, carbonates such as MgCO ₃ , CaCO ₃ , dolomite, metal sulfates like gypsum and heavy spar, natural and artificial silicates like talc, zeolites, wollastonil, feldspar, alumina like kaolin, rock dust, whiskers (whiskers), carbon fibers, man-made fibers or powders and soot. Viscosifying agents are, in particular, polymerizates having olefinically unsaturated groups, which can be "incorporated" into the polymer during polymerization. Such polymerizates are known and can be purchased, for example, under the brand name

. Other viscosity enhancers are polybutadiene, polyisoprene or polychlorobutadiene, as well as copolymers of butadiene, isoprene and chloroprene with olefins. Substances that increase the viscosity may be present in an amount of from 0.1 to 50 wt.%, Preferably from 1 to 30 and most preferably from 1 to 20 wt.% In terms of the amount of composition. When using fillers, it is advisable to maintain optical transparency for polymerization or to carry out the polymerization process in thin layers.

в сочетании с каталитическим количеством по меньшей мере одного термостабильного соединения молибдена (VI) или вольфрама (VI), содержащего по меньшей мере две метиловые группы или две однозамещенные метиловые группы, связанные с металлом, причем заместитель не содержит водородный атом в положении α ,
в) полимеризуют путем нагревания,
г) полимеризуют путем облучения,
д) полимеризуют путем нагрева и облучения,
е) активируют путем кратковременного нагрева однокомпонентного катализатора и заканчивают процесс полимеризации путем облучения, или
ж) активируют после кратковременного облучения однокомпонентный катализатор и завершают процесс полимеризации путем нагревания.Another subject of the invention is a method for producing cross-linked polymerizates as a result of metathesis polymerization, which is characterized in that the composition of
(a) at least one compound of formula I
(A) _n -B, (I)
where A denotes a radical of a hindered cycloolefin, B stands for a direct bond or an n-valent bridging group, and n represents an integer from 2 to 8, and
(b) a catalytic amount of at least one one-component polymerisation catalyst activated by heating or under the influence of light rays, with the exception of the (norbornene methyl) ester of norbornene carboxylic acid of the formula

in combination with a catalytic amount of at least one thermostable compound of molybdenum (VI) or tungsten (VI) containing at least two methyl groups or two monosubstituted methyl groups associated with the metal, the substituent not containing a hydrogen atom in position α,
c) polymerized by heating,
g) polymerized by irradiation,
d) polymerized by heating and irradiation,
e) activate by short-term heating of a single-component catalyst and complete the polymerization process by irradiation, or
g) activate, after short-term irradiation, a one-component catalyst and complete the polymerization process by heating.

Heating can occur at a temperature of from 50 to 300 ^o C, preferably from 60 to 250 ^o C, most preferably from 60 to 200 ^o C, and most preferably from 60 to 150 ^o C.

According to the claimed method, the reaction mixture is optionally irradiated throughout the reaction. If polymerization is initiated by the photochemical method, then the further course of the reaction occurs independently even in the dark. Advantageously, the irradiation is carried out by light waves having a length in the range from 50 to 1000 nm, preferably from 200 to 300 nm, and most preferably in the ultraviolet region. Exposure duration
depends on the type of light source. Suitable sources of irradiation are, for example, the sun, laser, X-ray and especially ultraviolet rays. According to the invention, ultraviolet lasers or ultraviolet lamps are advantageous. Irradiation of the catalyst can occur both before the addition of monomers, and during the addition, and also after it.

 The exposure time is from one second to several hours, in particular from a minute to hours. The sequence of the addition of monomers and catalyst is non-critical. The monomer can be placed in advance, and can also be added after the introduction of the catalyst. Also, the catalyst can be pre-irradiated, and then monomer can be added. In addition, a solution containing a catalyst and a monomer can also be irradiated.

 Irradiation, according to the claimed method, is carried out preferably at room temperature or slightly elevated. An increase in temperature increases the reaction rate. The used catalysts initiate only in exceptional cases at the selected temperatures of thermal polymerization with the formation of a polymer network. At temperatures selected to accelerate the reaction, photopolymerization occurs. However, it should be noted that the catalysts after a sufficient dose of radiation can be converted into thermoactive catalysts.

Irradiation, in accordance with the claimed method, is carried out, in particular, preferably at temperatures from -20 to +110 ^o C, most preferably from 20 to 80 ^o C.

 The exposure time depends mainly on the desired reaction. Short-term irradiation, for example, is chosen when the polymerization is initiated only by irradiation, and they want to complete by heating. Short-term exposure times are up to 60 s, preferably from 5 to 60 s, and most preferably from 10 to 40 s. A longer irradiation time is chosen, for example, when the polymerization is carried out mainly during irradiation, but they want to end when languishing.

 A completely special and unexpected advantage of the claimed method lies in the fact that the applied single-component catalysts after irradiation act as thermal catalysts. Hence, it becomes possible to continue and complete the polymerization process after short-term irradiation by applying heat, which brings with it great economic and technical benefits in various fields of manufacturing bodies by molding or coating.

The next subject of the invention are crosslinked polymerizates from at least one compound of formula I
(A) _n -B, (I)
where A represents a radical of a cycloolefin hindered, B stands for a direct bond or an n-valent bridging group, and n represents an integer from 2 to 8 and, if necessary, of other polymerizable monomers, with the exception of the norbornene methyl ester of norbornene carboxylic acid.

 Using the claimed method, it is possible to obtain materials for the manufacture of bodies by molding during processing by cutting or direct manufacture of such bodies of all kinds, as well as coatings and relief drawings (images).

 The claimed polymers can have completely different properties depending on the monomer used. Some are distinguished by very good oxygen permeability, low dielectric constants, good thermal stability and low water absorption; others exhibit exceptional optical properties, such as high transparency and low refractive indices. In addition, it should be noted, in particular, slight shrinkage. Therefore, they can find application in various fields of technology.

 The claimed compositions, as layers of carrier materials on surfaces, are characterized by high adhesion strength (adhesion). In addition, the applied materials are characterized by very high evenness and gloss of the surface. Among the good mechanical properties, in particular, insignificant shrinkage and high impact strength, as well as thermal stability, stand out. It should also be noted the possibility of easy removal of the product from the mold during molding and high resistance to solvents.

 Such polymers are suitable for the manufacture of medical devices, implants or constant lenses; for the manufacture of structural elements in electronics; as binders for the preparation of varnishes; as curable compounds in the manufacture of models or as adhesives for bonding substrates with low surface energy (for example, Teflon, polyethylene and polypropylene), and also as a photopolymerizable composition in stereolithography. The claimed compositions can also be used for the preparation of varnishes using photopolymerization, and can be used transparent, and even pigmented compositions. Both white and colored pigments can be used.

 The claimed compositions are particularly suitable for the manufacture of protective coatings and relief images. Another subject of the invention is a variant of the claimed method for producing layered materials or relief images on a carrier, in which the claimed composition and, if necessary, the solvent are applied as a layer on the carrier, for example by dipping, spreading, casting, rolling, squeezing or centrifugal casting, removing if necessary, using a solvent and treating the polymerization layer with light or heat rays, or using a photo frame, treating the layer with light rays, and then removing unirradiated particles ie with the solvent. After this, annealing can also be applied. In this way, it is possible to modify or create protection for the substrates or to make, for example, printed circuits, plate plates or pressure rolls. In the manufacture of printed circuits, the claimed compositions can be used as varnishes for soldering. Other possible applications are the manufacture of frames for screen printing, the use of printing inks as offset curable under the action of light rays for offset, screen and flexographic printing.

 In addition, the subject of the invention is a layer-coated carrier material, characterized in that a layer of the claimed composition is applied to the substrate.

 The subject of the invention is also a coated layer having a cured layer prepared from the claimed composition. Particularly emphasized is the extremely high adhesion strength of the layers even to metal surfaces, even if it is simply hydrocarbon polymerizates.

 Suitable carrier materials are, for example, those which consist of glass, minerals, ceramics, plastics, wood, semimetals, metals, metal oxides and metal nitrides. The thickness of the layers can be different, depending on the desire, and can be, for example, from 0.1 to 1000 μm, preferably from 0.5 to 500 μm, most preferably from 1 to 100 μm. Layered materials are characterized by high adhesion strength and good thermal and mechanical properties.

 Such materials can be obtained by known methods, such as, for example, coating, spraying, casting, for example centrifugal casting.

 The claimed compositions are also suitable for the production of polymers, such as rubber, or thermoplastic polymers, which can then become crosslinked if they contain reactive groups, such as, for example, (meth) acrylate or epoxy groups.

 The claimed compositions can be used in the same way as adhesives capable of curing under the influence of heat or light rays, for durable bonding of various materials, and excellent peeling resistance can be achieved.

 The claimed polymerizates, along with high adhesion strength, excellent processability, good surface properties (evenness, gloss), high crosslinking density and resistance to solvents and other liquids, are especially distinguished by good physical and mechanical properties, such as for example, temperature resistance, tensile and bending strength and impact strength, as well as excellent electrical properties, such as low surface stresses and charges (very low ε- and δ- nia). In addition, high oxygen permeability and limited water absorption should be mentioned. Only polymers derived from carbon and hydrogen are the most valuable from an environmental point of view, because they can be completely recycled, for example, by pyrolysis.

 The following are examples explaining the invention in more detail.

A) Preparation of biscycloolefins
Example A1: Preparation of compound N 0 (see EP 287762).

70 g (0.86 mol) of 1,5-hexadiene and 56 g (0.42 mol) of dicyclopentadiene were mixed in an autoclave and brought to 190 ^° C. over 8 hours. After cooling, the mixture was distilled in vacuo. At a temperature of from 80 to 110 ^o C and a pressure of from 0.28 to 0.30 mbar, 32.6 g (36%) of the product are obtained in the form of a colorless liquid;
n _D ²⁰ = 1.525.

Elementary analysis: Calculation C 89.65; H 10.35;
yield C 89.72; H 10.13.

 Example A2: Preparation of compound N 2.

35 g (0.32 mol) of 1,7-octadiene and 28 g (0.21 mol) of dicyclopentadiene are mixed in an autoclave and the mixture is brought to 190 ^° C. over 8 hours. After cooling, the mixture is distilled in vacuo. At a temperature of 100 ^° C. and a pressure of 0.21 mbar, 6.7 g (13%) of the product are obtained in the form of a colorless liquid; n _D ²⁰ = 1.516.

Elementary analysis: Calculation C 89.19; H 10.81;
yield C 89.50; H 10.60.

 Example A3: Preparation of compound N 3.

34.6 g (0.25 mol) of 1,5-decadiene and 33.1 g (0.25 mol) of dicyclopentadiene are mixed in an autoclave and the mixture is brought to 190 ^° C. for 8 hours. After cooling, the mixture is distilled in vacuo. At 80-100 ^° C. and a pressure of 0.24 mbar, 11.4 g (17%) of the product are obtained as a colorless liquid; n _{D 20} = 1,504, which hardens at room temperature.

Elemental analysis: Calculation C 88.82; H 11.18;
yield C 88.62; H 11.18.

 Example A4: Preparation of compound N 20.

99.7 g (0.40 mol) of cyanuric acid triallyl ester and 79.3 g (0.6 mol) of dicyclopentadiene are mixed in an autoclave and brought to a temperature of 190 ^o C. over 8 hours. After cooling, 160 g are obtained (89, 4%) a brown gummy solid with a melting point of 50 ^o C, soluble in toluene and chloroform.

 Elementary analysis: Calculation of C 72.46; H 7.43; 9.39.

 yield C, 72.21; H 7.52; 9.32.

A ') Preparation of Comonomers
Example A'1: Preparation of Compound N 59

100 g (0.92 mol) of 1,5-cyclooctadiene and 200 g (1.51 mol) of dicyclopentadiene are mixed in an autoclave with 0.4 g of hydroquinone monomethyl ether and adjusted to 190 ^° C. over 3 hours. After cooling, the mixture is distilled in a vacuum. At a temperature of 110 ^° C. and a pressure of 4.6 mbar, 73.5 g (33%) of the product are obtained as a colorless liquid; n _D ²⁰ = 1.534. MS: M ⁺ = 240.

Elementary analysis: Calculation C 89.92; H 10.08;
yield C 90.11; H 9.04.

 Example A'2: Preparation of Compound N 65

64.9 g (0.40 mol) of 1,5,9-cyclododecatriene and 79.3 g (0.60 mol) of dicyclopentadiene are stirred in an autoclave and brought to a temperature of 190 ^o C. over 8 hours. After cooling, the mixture is distilled in vacuo . At a temperature of from 50 to 60 ^° C. and a pressure of 0.04 mbar, 22.6 g (16%) of the product are obtained as a colorless liquid; n _D ²⁰ = 1.541. MS: M ⁺ = 360.

Elemental analysis: Calculation C 89.94; H 10.06;
yield C 89.96; H, 9.90.

 Example A'3: Preparation of compound N 63.

92.1 g (1.00 mol) of cycloheptatriene and 198.3 g (1.50 mol) of dicyclopentadiene are mixed in an autoclave and brought to a temperature of 190 ^° C. over 8 hours. After cooling, the mixture is distilled in vacuo. At a temperature of 75 ^° C. and a pressure of 0.12 mbar, 80.6 g (28%) of the product are obtained in the form of a colorless liquid; n _D ²⁰ = 1.542. MS: M ⁺ = 290.

Elemental analysis: Calculation C 90.98; H 9.02;
yield C, 90.71; H, 9.31.

 Example A'4: Preparation of Compound N 64

100 g (1.09 mol) of norbornadiene and 50 g (0.38 mol) of dicyclopentadiene are mixed in an autoclave with 0.2 g of hydroquinone monomethyl ether and the mixture is brought to 190 ^° C. over 3 hours. After cooling, the mixture is distilled in vacuo. At a temperature of 35 ^° C. and a pressure of 0.25 mbar, 25.0 g (29%) of the product are obtained in the form of a colorless liquid; n _D ²⁰ = 1.532. MS: M ⁺ = 224.

Elementary analysis: calculated C 91.01; H 8.99;
found C, 90.94; H 9.01.

 Example A'5: Preparation of Compound N 66

80.2 g (0.50 mol) of cyclododecene and 33.05 g (0.25 mol) of dicyclopentadiene are mixed in an autoclave and the mixture is brought to 190 ^° C for 8 hours. After cooling, the mixture is distilled in vacuo. At a temperature of 61 ^° C. and a pressure of 0.12 mbar, 8.10 g (7%) of the product are obtained in the form of a colorless liquid, n _D ²⁰ = 1.528. MS: M ⁺ = 232.

Elementary analysis: calculated C 87.86; H 12.14;
found C, 87.98; H 11.72.

 Example A'6: Preparation of compound N 68.

104.25 g (1.5 mol) of isoprene (98%), 208.7 g (1.5 mol) of dicyclopentadiene (95%) and 1.0 g of tertiary butyl pyrocatechol are mixed in an autoclave and stirred for 8 hours in the presence of N ₂ , brought to a temperature of 200 ^o C. After cooling, the semi-solid mass is distilled in a high vacuum. Mp: 60 ^° C (0.07 mbar). Yield: 202.4 g (67.4%). n _D ²⁰ = 1.53.

Elementary analysis: calculated C 89.94; H 10.06;
found C, 89.85; H 10.08.

 Example A'7: Preparation of compound N 69.

139.2 g (1.0 mol) of dicyclopentadiene (95%), 194.2 g (2.0 mol) of 2-norbornene (97%) and 3.0 g of tertiary butyl pyrocatechol are mixed in an autoclave and stirred for 2 hours in the presence of N ₂ , brought to a temperature of 230 ^o C. After cooling, the semi-solid mass is distilled in a high vacuum. Mp: 65 ^° C (0.065 mbar). Exit; 69.0 g (21.5%). n _D ²⁰ = 1.54.

Elementary analysis: calculated C 89.93; H 10.07;
found C, 90.07; H 9.88.

B) Obtaining cross-linked polymerizates
As catalysts are used:
A) W (= NC ₆ H ₅ ) [OC (CH ₃ ) ₃ ] CH ₂ Si ((CH ₃ ) ₃ ] ₂ Cl
B) W (= NC ₆ H ₅ ) [OCCH ₃ (CF ₃ ) ₂ ] CH ₂ Si ((CH ₃ ) ₃ ] ₂
C) RuCl ₂ (p-cumene) P (C ₆ H ₁₁ ) ₃
Example B1:
The compound of Example A1 was mixed with catalyst A (0.7% by weight) and the mixture was poured into a glass mold. Then, it is subjected to ultraviolet irradiation in a furnace (4 tubes with a power of 100 W) for 30 minutes at room temperature, after which thermal polymerization is carried out for 1 hour at a temperature of 80 ^° C. A plate with a T _g 75 ^o C (not changing shape) is obtained (determined by Differential Scanning Calometrie). The polymer swells in toluene without dissolving. A low swelling coefficient of 44% indicates a high density of network formation.

Example B2:
The mixture from Example B1 is irradiated with only one 200W medium pressure mercury vapor lamp. A plate with a constant shape with a T _{g of} 60 ^° C is obtained. The swelling coefficient in toluene is 54%.

Example B3:
Work as in example B1, but with one weight% of the catalyst, using additional heat treatment for subsequent hardening at 100 ^o C for 30 minutes Get a plate that does not change its shape, having a density of 1.06 g / cm ³ ; T _g 125 ^o C, the modulus of elasticity is 2210 N / mm ² . Shore stiffness is 85, and the swelling coefficient in toluene is 54%.

Example B4:
The compound of Example A1 was mixed with catalyst B (1 wt.%) And poured into a glass mold. For 2 hours at room temperature, they were kept in an oven under ultraviolet rays in accordance with Example B1, and then polymerized for 30 minutes at 80 ^° C, 30 minutes at 100 ^° C and 30 minutes at 120 ^° C. A shapeless plate with a density of 1 was obtained. 06 g / cm ³ , T _g 125 ^o C and elastic modulus 2390 N / mm ² . The maximum elasticity is 40.4 N / mm ² , the maximum elongation is 2.0% and the Charpy impact strength is 8.9 kJ / m ² . The swelling coefficient in toluene is 2000%.

Examples B5 through B13:
The monomer obtained according to the example is mixed with catalyst C (0.5 wt.%) And poured into a glass mold. They are thermally cured for 1 hour at 60 ^° C, 1 hour at 80 ^° C, 1 hour at 100 ^° C and 2 hours at 120 ^° C. Additional curing occurs within 2 hours at 150 ^° C. The results are given in the table.

Claims (27)

1. The composition for producing metathesis polymers from
a) at least one compound of formula I
(A) _n -B
where A is a radical of a cycloolefin hindered;
B denotes a direct link or a bridging group
-X ₅ -R ₂₀ -X ₆ -,
where X ₅ and X ₆ independently of each other denote a direct connection;
R ₂₀ is C ₂ -C ₁₈ alkylene unsubstituted or substituted with C ₁ -C ₁ alkyl, or C ₇ -C ₁₉ aralkylene;
n is an integer from 2 to 8,
b) a catalytic amount of at least one thermo- or radioactive one-component catalyst, with the exception of norbornene methyl ester of norbornene carboxylic acid of the formula

in combination with a catalytic amount of at least one heat-resistant compound of molybdenum (VI) or tungsten (VI) containing at least two methyl groups or two monosubstituted methyl groups associated with the metal, and the substituent does not contain a hydrogen atom in position α.  2. The composition according to claim 1, characterized in that the hindered cycloolefins are monocyclic or polycyclic fused ring systems and / or bridged ring systems that are not substituted or substituted and which may contain O, S, N or Si heteroatoms in one or multiple rings and / or fused alicyclic, aromatic or heteroaromatic rings.  3. The composition according to p. 2, characterized in that the individual cyclic rings contain from 3 to 16 ring elements.  4. The composition according to claim 2, characterized in that the cyclic rings contain from 3 to 12 ring elements.  5. The composition according to claim 2, characterized in that the cyclic rings contain from 3 to 8 ring elements. 6. The composition according to claim 1, characterized in that the radical of the hindered cycloolefin corresponds to formula II

where Q ₁ denotes a radical with at least one carbon atom, which forms together with the group - CH = CQ ₂ one at least a three-membered alicyclic ring containing, under certain conditions, one or more heteroatoms selected from the group consisting of silicon, phosphorus, oxygen, nitrogen and sulfur; and which is not substituted or substituted by halogen, = O, —CN, —NO ₂ -, R ₁ R ₂ R ₃ Si— (O) _u -, —COOM, —SO ₃ M, PO ₃ M, —COO (M ₁ ) _1/2 , -SO ₃ (M _1/2 ), -PO ₃ (M ₁ ) _1/2 , C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ hydroxyalkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₆ cyanoalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₆ aryl, C ₇ -C ₁₆ aralkyl,
C ₃ -C ₆ heterocycloalkyl, C ₃ -C ₁₆ heteroaryl, C ₄ -C ₁₆ heteroaralkyl or R ₄ - X, or in which two adjacent carbon atoms are substituted with -CO-O-CO- or -CO-NR ₅ -CO-; or in which, under certain conditions, one aromatic or heteroaromatic ring and / or other alicyclic rings unsubstituted or substituted by halogen are condensed at adjacent carbon atoms of the alicyclic ring, —CN, —NO ₂ , R ₆ R ₇ R ₈ Si- (O) _u - , -COOM, -SO ₃ M, -RO ₃ M, -COO (M ₁ ) _1/2 , -SO ₃ (M ₁ ) _1/2 , -PO ₃ (M ₁ ) _1/2 , C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -hydroxyalkyl, C ₁ -C ₂₀ -haloalkyl, C ₁ -C ₆ -cyanoalkyl, C ₃ -C ₈ -cycloalkyl, C ₆ -C ₁₆ -aryl, C ₇ -C ₁₆ - aralkyl, C ₃ -C ₆ heterocycloalkyl, C ₃ -C ₁₆ heteroaryl, C ₄ -C ₁₆ heteroalkyl or R ₁₃ -X ₁ -;
X and X _{1 are} independently of each other instead of -O-, -S-, -CO-, -SO-, SO ₂ -, -OC (O) -, -C (O) -O-, -C (O ) -NR ₅ -, NR ₁₀ -C (O) -, -SO ₂ -O-or-O-SO ₂ -;
R ₁ , R ₂ and R _{3 are} independently C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ perfluoroalkyl, phenyl or benzyl;
R ₄ and R _{13 are} independently C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₂₀ hydroxyalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₆ aryl, C ₇ -C ₁₆ aralkyl;
R ₅ and R _{10 are} independently hydrogen, C ₁ -C ₁₂ alkyl, phenyl or benzyl, the alkyl groups being, in turn, unsubstituted or substituted with C ₁ -C ₁₂ alkoxy or C ₃ -C ₈ - cycloalkyl;
R ₆ , R ₇ and R _{8 are} independently C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ perfluoroalkyl, phenyl or benzyl;
M stands for alkali metal, and M ₁ stands for alkaline earth metal; and u = 0 or 1;
moreover, the alicyclic ring formed with Q contains, under certain conditions, other, non-aromatic double bonds;
Q ₂ is hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₂₀ alkoxy, halogen, —CN or R ₁₁ —X ₂ -;
R ₁₁ is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₂₀ hydroxyalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₆ aryl or C ₇ -C ₁₆ aralkyl ;
X ₂ represents - C (O) —O— or —C (O) —NR ₁₂ -;
R ₁₂ is hydrogen, C ₁ -C ₁₂ alkyl, phenyl or benzyl;
moreover, the above-mentioned groups of cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl are unsubstituted or substituted by C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, -NO ₂ , -CN or halogen, and wherein the heteroatoms of the above heterocycloalkyl groups and heteroaralkyl are selected from the group —O—, —S—, NR ₉ - and —N =;
R ₉ is hydrogen, C ₁ -C ₁₂ alkyl, phenyl or benzyl. 7. The composition according to claim 6, characterized in that in formula II Q ₂ denotes hydrogen. 8. The composition according to claim 6, characterized in that in formula II the alicyclic ring formed with Q ₁ together with the group CH = CQ ₂ - has from 3 to 8 ring atoms, moreover, it is a monocyclic, bicyclic, tricyclic or tetracyclic ring system. 9. The composition according to claim 6, characterized in that the radical of the hindered cycloolefin corresponds to formula II, where Q ₁ denotes a radical with at least one carbon atom, which forms together with the group - CH = CQ ₂ one at least three-twenty-fold alicyclic ring, containing, under certain conditions, one or more heteroatoms selected from the group consisting of silicon, oxygen, nitrogen and sulfur; and which is not substituted or substituted by halogen, = O, —CN, —NO ₂ , R ₁ R ₂ R ₃ Si- (O) _u -, —COOM, —SO ₃ M, —RO ₃ M, —COO (M ₁ ) _1/2 , -SO ₃ (M ₁ ) _1/2 , -PO ₃ (M ₁ ) _1/2 , C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ hydroxyalkyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₄ cyanoalkyl, C ₃ -C ₆ cycloalkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₂ aralkyl, C ₃ -C ₆ heterocycloalkyl, C ₃ -C ₁₂ heteroaryl, C ₄ —C ₁₂ -heteroaralkyl or R ₄ —X, or in which two adjacent carbon atoms in this radical Q ₁ are substituted with —CO — O — CO— or —CO — NR ₅ —CO—; or which, under certain conditions, an aromatic or heteroaromatic ring and / or other alicyclic rings unsubstituted or substituted by halogen, —CN, —NO ₂ , R ₆ R ₇ R ₈ Si—, —COOM, —SO ₃ M are condensed at adjacent carbon atoms , -RO ₃ M, -COO (M ₁ ) _1/2 , -SO ₃ (M ₁ ) _1/2 , -PO ₃ (M ₁ ) _1/2 , C ₁ -C ₁₂ -alkyl, C ₁ -C _12- hydroxyalkyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₄ cyanoalkyl, C ₃ -C ₆ cycloalkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₂ aralkyl,
C ₃ -C ₆ heterocycloalkyl, C ₃ -C ₁₂ heteroaryl, C ₄ -C ₁₂ heteroalkyl or R ₁₃ -X ₁ -; X and X _{1 are} independently of each other instead of -O-, -S-, -CO-, -SO-, SO ₂ -, -OC (O) -, -C (O) -O-, -C (O ) -NR ₅ -, NR ₁₀ -C (O) -, -SO ₂ -O- or -O-SO ₂ -; R ₁ , R ₂ and R _{3 are} independently C ₁ -C ₆ alkyl, C ₁ -C ₆ perfluoroalkyl, phenyl or benzyl; R ₄ and R _{13 are} independently C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₁₂ hydroxyalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₂ aralkyl; R ₅ and R _{10 are} independently hydrogen, C ₁ -C ₆ alkyl, phenyl or benzyl, the alkyl groups being, in turn, unsubstituted or substituted with C ₁ -C ₆ alkoxy or C ₃ -C ₆ - cycloalkyl; R ₆ , R ₇ and R _{8 are} independently C ₁ -C ₆ alkyl, C ₁ -C ₆ perfluoroalkyl, phenyl or benzyl; M stands for alkali metal, and M ₁ stands for alkaline earth metal; u = 0 or 1, and the alicyclic ring formed with Q contains, under certain conditions, other, non-aromatic double bonds; Q ₂ is hydrogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₆ alkoxy, halogen, —CN or R ₁₁ —X ₂ -; R ₁₁ is C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₁₂ hydroxyalkyl, C ₃ -C ₆ cycloalkyl, C ₆ -C ₁₂ aryl or C ₇ -C ₁₂ aralkyl ; X ₂ represents - C (O) —O— or —C (O) —NR ₁₂ -; R ₁₂ is hydrogen, C ₁ -C ₆ alkyl, phenyl or benzyl; moreover, the above-mentioned groups of cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl are unsubstituted or substituted by C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxyl, -NO ₂ , -CN or halogen, and moreover, heteroatoms of the above heterocycloalkyl groups and heteroaralkyl are selected from the group —O—, —S—, NR ₉ - and —N =; R ₉ is hydrogen, C ₁ -C ₆ alkyl, phenyl or benzyl. 10. The composition according to claim 6, characterized in that the hindered cycloolefin radical corresponds to formula II, where Q ₁ denotes a radical with at least one carbon atom, which forms, together with the group -CH = CQ _{2 a} 3-10 membered alicyclic ring, containing, under certain conditions, one heteroatom selected from the group consisting of silicon, oxygen, nitrogen and sulfur; and which is not substituted or substituted by halogen, —CN, —NO ₂ , R ₁ R ₂ R ₃ Si—, —COOM, —SO ₃ M, —RO ₃ M, —COO (M ₁ ) _1/2 , —SO ₃ M ₁ ) _1/2 , -PO ₃ (M ₁ ) _1/2 , C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₄ cyanoalkyl, With ₃ -C ₆ -cycloalkyl, phenyl, benzyl or R ₄ - X-, or in which, under certain conditions, an adjacent aromatic ring has a condensed aromatic or heteroaromatic ring unsubstituted or substituted by halogen, —CN, —NO ₂ , R ₆ R ₇ R ₈ Si-, -COOM, -SO ₃ M, -PO ₃ M, -COO (M ₁ ) _1/2 , -SO ₃ (M ₁ ) _1/2 , -PO ₃ M ₁ ) _1/2 , С C ₁ -C ₆ -alkyl, C ₁ -C ₆ -gidroksialkilom, C ₁ -C ₆ haloalkyl, C ₁ -C ₄ -cyano lkilom, C ₃ -C ₆ -cycloalkyl, phenyl, benzyl or R ₁₃ -X ₁ -; R ₁ , R ₂ and R _{3 are} independently C ₁ -C ₄ alkyl, C ₁ -C ₄ perfluoroalkyl, phenyl or benzyl; M stands for alkali metal, and M ₁ stands for alkaline earth metal; R ₄ and R _{13 are} independently C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ hydroxyalkyl or C ₃ -C ₆ cycloalkyl; X and X _{1 are} independently of each other instead of —O—, —S—, —CO—, —SO—, SO ₂ -, R ₆ , R ₇ and R _{8 are} independently C ₁ -C ₄ -alkyl C ₁ -C ₄ perfluoroalkyl, phenyl or benzyl; Q ₂ is hydrogen.  11. The composition according to claim 6, characterized in that with respect to the cycloolefin radical of formula II, it is an unsubstituted or substituted cyclopropenyl, cyclobutenyl, cyclopentenyl, cycloheptenyl, cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl or norbornene. 12. The composition according to claim 6, characterized in that the cycloolefin radical of formula II is a radical of formula III

where X ₃ denotes - CHR ₁₆ -, oxygen or sulfur; R ₄ and R _{5 are} independently hydrogen, —CN, trifluoromethyl, (CH ₃ ) ₃ Si — O—, (CH ₃ ) ₃ Si— or —COOR ₁₇ ;
R ₁₆ and R ₁₇ independently from each other represent hydrogen, C ₁ -C ₁₂ -alkyl, phenyl or benzyl;
or formula IV

where X ₄ designates - CHR ₁₉ -, oxygen or sulfur;
R ₁₉ represents hydrogen, C ₁ -C ₁₂ alkyl, phenyl or benzyl;
R ₁₈ is hydrogen, C ₁ -C ₆ alkyl or halogen. 13. The composition according to p. 6, characterized in that the cycloolefin radical of the formula II is norbornenyl of the formula

14. The composition according to claim 6, characterized in that it contains a heat-resistant compound of ruthenium or osmium as a one-component catalyst, which contains at least one photolabile ligand bound to a ruthenium or osmium atom, and in which the remaining coordination sites are saturated with non-photolabile bound groups. 15. The composition according to p. 14, characterized in that the compounds of ruthenium and osmium correspond to the formula X
[L ₁ Me (L ₈ ) ₅ ] ²⁺ [Y ₁ ^x- ] _2x where L ₁ is a photolabile linked group;
L ₈ is a non-photolabile linked group;
Me represents Ru or Os, Y ₁ is an uncoordinated anion,
x = 1.2 or 3.  16. The composition according to claim 6, characterized in that the one-component catalyst is a compound of molybdenum (VI) or tungsten (VI), which contains at least two methyl groups or two monosubstituted methyl groups associated with the metal, and the Deputy does not contain any hydrogen atom in position α. 17. The composition according to p. 16, characterized in that, under certain conditions, monosubstituted methyl groups associated with the metal correspond to the formula XI
-CH ₂ -R
where R represents H, —CF ₃ , —SiR ₃₈ R ₃₉ R ₄₀ , CR ₄₁ R ₄₂ R ₄₃ , unsubstituted or substituted with C ₁ C ₆ alkyl or C ₁ -C ₆ alkoxyl C ₆ -C ₁₆ aryl or C ₄ -C ₁₅ heteroaryl with 1 to 3 heteroatoms from the group O, S or N;
R ₃₈ , R ₃₉ , R _{40 are} independently C ₁ -C ₆ alkyl, C ₅ or C ₆ -cycloalkyl, or unsubstituted or substituted with C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy phenyl or benzyl;
R ₄₁ , R ₄₂ , R _{43 are} independently C ₁ -C ₁₀ -alkyl which is unsubstituted or substituted by C ₁ -C ₁₀ -alkoxyl, or R ₄₁ and R ₄₂ have this meaning, and R ₄₃ is C ₆ -C ₁₀ aryl or C ₄ -C ₉ heteroaryl, which is unsubstituted or substituted by C ₁ C ₆ alkyl or C ₁ -C ₆ alkoxyl.  18. The composition according to claim 6, characterized in that the one-component catalyst is a thermostable compound of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI), in which the silylmethyl group and at least one halogen bonded to metal. 19. The composition according to p. 18, characterized in that the silylmethyl group corresponds to the formula XIV
-CH ₂ -SiR ₃₈ R ₃₉ R ₄₀
where R ₃₈ , R ₃₉ , R _{40 are} independently C ₁ -C ₁₈ -alkyl, C ₅ - or C ₆ -cycloalkyl, or unsubstituted or substituted with C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxyl phenyl or benzyl.  20. The composition according to claim 6, characterized in that the one-component catalyst is a compound of niobium (V) or tantalum (V), which contains at least two methyl groups or two monosubstituted methyl groups associated with the metal, and the Deputy does not contain a hydrogen atom in position α. 21. The composition according to claim 20, characterized in that, under certain conditions, monosubstituted methyl groups correspond to the formula XI
-CH ₂ -R
where R is H, —CF ₃ , —SiR ₃₈ R ₃₉ R ₄₀ , CR ₄₁ R ₄₂ R ₄₃ , unsubstituted or substituted with C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxyl C ₆ -C ₁₆ aryl or C ₄ -C ₁₅ heteroaryl with 1-3 heteroatoms from the group O, S and N;
R ₃₈ , R ₃₉ , R _{40 are} independently C ₁ -C ₆ alkyl, C ₅ or C ₆ -cycloalkyl, or unsubstituted or substituted with C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy phenyl or benzyl;
R ₄₁ , R ₄₂ , R _{43 are} independently C ₁ -C ₁₀ -alkyl, which is unsubstituted or substituted by C ₁ -C ₁₀ -alkoxyl, or R ₄₁ and R ₄₂ have this meaning, and R ₄₃ is C ₆ -C ₁₀ aryl or C ₄ -C ₉ heteroaryl, which is unsubstituted or substituted by C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy.  22. The composition according to claim 6, characterized in that the one-component catalyst is a titanium compound (IV), which contains at least two methyl groups or two monosubstituted methyl groups associated with the metal, and the Deputy does not contain a hydrogen atom in position α. 23. The composition according to p. 22, characterized in that, under certain conditions, monosubstituted methyl groups correspond to the formula XI
-CH ₂ -R
where R is H, —CF ₃ , —SiR ₃₈ R ₃₉ R ₁₀ , CR ₄₁ R ₄₂ R ₄₃ , unsubstituted or substituted with C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxyl C ₆ -C ₁₆ aryl or C ₄ -C ₁₅ heteroaryl with 1-3 heteroatoms from the group O, S and N;
R ₃₈ , R ₃₉ , R ₁₀ independently are C ₁ C ₆ alkyl, C ₅ or C ₆ cycloalkyl, or unsubstituted or substituted with C ₁ C ₆ alkyl or C ₁ -C ₆ alkoxy phenyl or benzyl ;
R ₄₁ , R ₄₂ , R _{43 are} independently C ₁ -C ₁₀ alkyl which is unsubstituted or substituted by C ₁ -C ₁₀ alkoxyl, or R ₄₁ and R ₄₂ have this meaning, and R ₄₃ is C ₆ -C ₁₀ aryl or C ₄ -C ₉ heteroaryl, which is unsubstituted or substituted with C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy.  24. The composition according to claim 6, characterized in that the one-component catalyst is a ruthenium or osmium compound that contains at least one phosphine group, at least one photolabile group and, under certain conditions, a neutral group bound to a metal atom, and there are from 2 to 5 linked groups, and which contains acid anions to equalize the charge. 25. The composition according to paragraph 24, wherein the phosphine linked groups correspond to formulas XXIII or XXIIIa
PR ₉₁ R ₉₂ R ₉₃
R ₉₁ R ₉₂ PZ ₁ -PR ₉₁ R ₉₂
where R ₉₁ , R ₉₂ , R _{93 are} independently H, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl or C ₁ -C ₆ alkoxy C ₄ -C ₁₂ cycloalkyl, either unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl or C ₁ -C ₆ alkoxyl C ₆ -C ₁₆ aryl, or unsubstituted or substituted with C ₁ C _6- alkyl, C ₁ -C ₆ haloalkyl or C ₁ -C ₆ alkoxyl C ₇ -C ₁₆ aralkyl; the radicals R ₉₁ and R ₉₂ together represent unsubstituted or substituted C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl or C ₁ -C ₆ -alkoxyl tetra- or pentamethylene, or unsubstituted or substituted by C ₁ -C ₆ -alkyl , C ₁ -C ₆ haloalkyl or C ₁ -C ₆ alkoxyl fused with one or two 1,2-phenylenes is tetra- or pentamethylene, and R ₉₃ is as defined above;
Z ₁ is unsubstituted or substituted C ₁ -C ₄ alkoxy of C ₂ -C ₁₂ straight or branched chain alkylene, unsubstituted or substituted with C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy 1,2- or 1 , 3 - cycloalkylene with carbon atoms in an amount of from 4 to 8, or unsubstituted or substituted with C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxyl 1,2 - or 1,3-heterocycloalkylene with five or six ring elements and one heteroatom from the group O or N. 26. The composition according to claim 6, characterized in that the one-component catalyst is a divalent cationic compound of ruthenium or osmium with a metal atom to which 1 to 3 tertiary phosphine groups are attached with substituents requiring space, in the case of a ruthenium compound, under certain conditions non-photolabile neutral groups and associated anions for charge equalization, with the proviso that in (trisfenilfosfin) dihalides or hydride halides the phenyl groups ruthenium substituted c ₁ -C ₁₈ -alkyl, c ₁ -C ₁₈ haloalkyl Is C ₁ -C ₁₈ alkoxy. 27. The composition according to p. 26, wherein the phosphine linked groups correspond to formulas XXIII or XXIIIa
PR ₉₁ R ₉₂ R ₉₃
R ₉₁ R ₉₂ PZ ₁ -PR ₉₁ R ₉₂
where R ₉₁ , R ₉₂ , R _{93 are} independently H, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl or C ₁ -C ₆ alkoxy C ₄ -C ₁₂ cycloalkyl, either unsubstituted or substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl or C ₁ -C ₆ alkoxy, C ₆ -C ₁₆ aryl, or unsubstituted or substituted C ₁ - C ₆ -alkyl, C ₁ -C ₆ haloalkyl or C ₁ -C ₆ alkoxyl C ₇ -C ₁₆ aralkyl; the radicals R ₉₁ and R ₉₂ together represent unsubstituted or substituted C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl or C ₁ -C ₆ -alkoxyl tetra- or pentamethylene, or unsubstituted or substituted by C ₁ -C ₆ -alkyl , C ₁ -C ₆ haloalkyl or C ₁ -C ₆ alkoxyl fused with one or two 1,2-phenylenes is tetra- or pentamethylene, and R ₉₃ is as defined above;
Z ₁ is unsubstituted or substituted C ₁ -C ₄ alkoxy of C ₂ -C ₁₂ straight or branched chain alkylene, unsubstituted or substituted with C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy 1,2- or 1 , 3-cycloalkylene with carbon atoms in an amount of from 4 to 8, or unsubstituted or substituted by C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy 1,2- or 1,3-heterocycloalkylene with five or six ring elements and one heteroatom from the group O or N.  28. The composition according to claim 6, characterized in that the one-component catalyst is contained in an amount of 0.001 to 20 mol.% In terms of the amount of monomer.

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