CN1146569C

CN1146569C - Dialkylmethylene bridged fluorenyl cyclopentadiene rare-earth complex and its preparing process and application

Info

Publication number: CN1146569C
Application number: CNB001252038A
Authority: CN
Inventors: 钱长涛; 聂万丽
Original assignee: Shanghai Institute of Organic Chemistry of CAS
Current assignee: Shanghai Institute of Organic Chemistry of CAS
Priority date: 2000-09-15
Filing date: 2000-09-15
Publication date: 2004-04-21
Anticipated expiration: 2020-09-15
Also published as: CN1286256A

Abstract

The present invention relates to a dialkyl methylene bridged fluorenyl cyclopentadienyl rare earth coordination compound with the following molecular formula, a synthetic method and a purpose of catalysts thereof. The dialkyl methylene bridged fluorenyl cyclopentadienyl rare earth coordination compound has the molecular formula of {[X1]2R7(C5R1R2R3R4)(C13H6R5R6)}[MX2(L)n]m; in the molecular formula, R1, R3 or R4 are H or CH3; R2 is H or C1-4 alkyl; R5 or R6 is H, G-4 alkyl or Si(CH3)3; R7 is Si, C, Ge or Sn; X<1> is C1 to 4 alkyl or phenyl; X<2> is Cl, BH, C1 to 4 alkyl, N[(CH3)3Si]2, CH[(CH3)3Si]2, CH2[(CH3)3Si] or tetrahydrofuran (THF); M is lanthanides, yttrium or scandium; L is (CH3)3Si, Li(THF)4, [Y-crown ether] or [Y-crown ether]-2, 4-epoxy hexacyclic ring; n is equal to 1 or 0 and m is equal to 1 or 2; when m is equal to 2, n is equal to 0; Y is univalent metal; crown ether is 18-crown ether-6 or 15-crown ether-5.

Description

A kind of dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding, synthetic method and purposes

The present invention relates to a kind of rare earth organic and learn, specifically a kind of phenylmethylene bridged fluorenyl cyclopentadiene base rare earth compounding, synthetic method and as the purposes of the catalyzer of polyreaction.

Organometallic Chemistry and catalysis are one of fields, forward position of contemporary chemistry, and the Organometallic Chemistry of rare earth element has been subjected to special attention.Lanthanon comprises ten five elements of ordination number 57 to 71, and scandium and yttrium are close with lanthanon by its character, and in nature and its symbiosis, these 17 elements are referred to as rare earth element.Because the 4f track of rare earth metal is compared with 5d with normal valency electronic orbit 6s, 6p, is in internal layer, a little less than the big and ligand trajectory of the shielding effect that is subjected to interacted, bonding power was relatively low, so the vitochemical development of rare earth metal was once once slow.Along with modern experimental technique and analysis means constantly develop, rare earth organic compounds could synthesize evaluation according to the reaction of routine.The later stage seventies has obtained launching rapidly to the research of rare earth organic compounds, at first be found several quasi-representatives have a rare earth element series feature valence state Ln ³⁺Rare earth compound, and then expand to and have Ln ⁰, Ln ²⁺, Ln ⁴⁺The rare earth element of oxidation state.These organometallic compounds are used as typical agents and are used for organic synthesis, or are used as highly active catalyzer.Make the rare earth metal organic chemistry demonstrate the potential application prospect.

Rare earth organic compounds plays an important role in the formation of homogeneous catalysis C-H, C-C, C-X key.At present, most of all stable by cyclopentadienyl or its analogue about the work of rare earth organic compounds, wherein alkylate or hydride are all showing higher activity aspect catalyzer or stoichiometric reaction reagent.General connect cyclopentadienyl ligands or change substituting group on it, all can significantly improve its catalytic activity.For metal complexes, coordination environment is all very important to its reactive behavior, especially to rare earth metal complex, because the 4f valence orbit is subjected to the bigger shielding effect of inner orbital, make when it becomes key with part, static factor and steric factor are often even more important than interorbital interaction, so coordination environment is to its reactive decisive role.Its formed title complex character and d district title complex character have bigger difference, so rare earth metal complex has its particular structure and reactive behavior.Because the expansion of 4f track is limited, make its role in rare earth compounding big not as the effect of d track in the transition metal, therefore, the influence of part becomes more important.Want to bring into play more fully the rare earth reactive chemistry, just must regulate the metal coordination environment of part on every side effectively.

To so far, cyclopentadienyl ligands is occupied critical role always in the rare earth metal organic chemistry.Cyclopentadienyl is considered to assistant ligand in muriate, it does not participate in reaction generally speaking, and the Cp base can make muriatic solvability and stability improve, and makes and can study the chemical reaction of Ln-Z key.Two cyclopentadienyltitanium trichloride things are synthetic contain Ln-C, the important as precursors of the isodesmic rare earth metal organic coordination compound of Ln-H and Ln-N.1980, Evans etc. utilized sterically hindered bigger pentamethyl-cyclopentadiene to synthesize [(CH as part ₃) ₅C ₅] ₂Nd (μ-Cl) ₂Li (THF) ₂Rare earth compounding (Inorg.Chem., 19,2190,1980).Since then, the pentamethyl-cyclopentadiene becomes the most frequently used part, considerably beyond previously used unsubstituted cyclopentadienyl, makes the research of rare earth two half metallocenes obtain bigger development.1981, Lappert was with C ₅H ₃(SiMe ₃) ₂As part, under different conditions, stable light rare earths two half metallocene { Ln[C have successfully been synthesized ₅H ₂(SiMe ₃) ₂] ₂Cl} and [C ₅H ₂(SiMe ₃) ₂] ₂Ln (μ-Cl ₂) Li (THF) ₂(Ln=La, Pr Nd), and use X-ray single crystal diffraction to measure their crystalline structure (J.Chem.Soc., Chem.Commun., 1190,1981).

The bridging dicyclopentadiene is that a class ideal is stablized the muriatic part of light rare earths cyclopentadienyl.Because bridge linking effect reduces the degree of freedom of luxuriant ring, the geometry of metallocene changes, a part is comparatively crowded around the metal, other parts are comparatively loose, title complex is not only stablized, central metallic ions also has bigger reaction contact surface simultaneously, makes this class title complex become the high catalyzer of a class catalytic activity.Especially the space of monatomic bridging dicyclopentadienyl part around can bigger ground expanded metal ion, the more accessible central metallic ions of reaction substrate, the reactive enhancing.1980, we cooperated with Tsutsui, used C ₅H ₅CH ₂CH ₂CH ₂C ₅H ₅Make the hydrocarbon rare earth compounding that part has successfully synthesized the light rare earths muriate and contained σ-key, avoided the disproportionation reaction (J.Organomet Chem., 263,333,1984) of light rare earths title complex effectively.A series of novel bridge ligands have been developed subsequently again, as C ₅H ₅CH ₂C ₆H ₄CH ₂C ₅H ₅, C ₅H ₅CH ₂CH ₂OCH ₂C ₅H ₅And C ₅H ₅CH ₂CH ₂NCH ₃CH ₂CH ₂C ₅H ₅, they have stablized light rare earths two cyclopentadienyltitanium trichloride things preferably, and corresponding rare earth compounding also has high reaction activity and high (J.Organomet.Chem., 299.97,1986; InorganicChimica Acta, 139,195,1987; L Polyhydron, 9,479,1990)

In recent years, existing reported in literature rare earth metallocene complex can be used as the catalyzer of polarity and non-polar monomer living polymerization, and obtain the polymkeric substance of high molecular weight and narrow molecular weight distribution, although two components, three catalytic systems are still used in the polyreaction widely, replace possible (H.Yasuda etc., Bull.Chem.Soc.Jpn., 70 of single component catalyst system in the near future with becoming, 1745,1977).

Along with fourth officer family metallocene catalyst is used for olefinic polyreaction, the activity that the rare earth metallocene complex is shown in to ethene, alpha-olefin, polar monomer and many organic reactions makes people produce great interest to it.In fourth officer family catalyst system, comprising various informative cyclopentadienyl derivative part.As, the cyclopentadienyl of cyclopentadienyl, replacement, indenyl and fluorenyl etc.By comparison, the synthetic method of rare earth metallocene is but very limited.This makes and disproportionation easily takes place the rare earth compounding instability or at metal center complexing solvent molecule, reactive behavior is reduced mainly owing to strong Lewis acidity, heavy ion radius and the lower covalent linkage of rare earth ion.People are in order to overcome these problems and further to understand in the rare earth compounding π-part in whole molecular geometry of control and electrical property role, in the metallocene catalyst system at luxuriant ring substituents, fluorenyl ligand shows unique effect in the polyreaction of alkene.Synthetic and the structure (W.J.Evani. etc. of the title complex of two fluorenyl divalence samariums have only been reported at present in the document, Organome tallics, 13,1281,1994) and many fluorenyls title complex of trivalent yttrium and lanthanum synthetic, the latter's structure is not also determined (R.K.Sharma etc., J.Indian Chem.Soc., 64,506,1987).Contain synthetic, the structure of rare earth compounding of fluorenyl ligand and catalytic activity effect etc. and all also do not obtain due illustrating.

Reaction yet there are no report about the symmetric catalyzed by rare-earth complex MIMA of Cs-polymeric, in conjunction with our expansion to the work of bridging organic RE metallocene complex study on the synthesis, the many-sided factors such as different bridging atoms and substituting group of considering design the synthetic symmetric monatomic bridged fluorenyl cyclopentadiene base rare earth compounding of Cs-that has to the issuable influence of complex structure reactivity worth.Hope characterizes its structural performance, investigates the activity of their catalysis alpha-olefins and polar monomer polyreaction, and further understands the influence relation of the structure of organic RE metallocene complex to micmstructure of polymer.Not only certain meaning is arranged, also have the potential using value enriching the rare earth compounding chemistry.

The object of the invention provides a kind of dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compound.

Another purpose of the present invention provides a kind of synthetic method of synthetic above-mentioned dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding.

The object of the invention also provides a kind of purposes of above-mentioned dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding.

Dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding of the present invention has { [(X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶)] MX ²(L) _n} _mMolecular formula, R wherein ¹, R ³Or R ⁴=H or CH ₃, R ²=H or C _1-4Alkyl, R ⁵Or R ⁶=H, C _1-4Alkyl or Si (CH ₃) ₃, R ⁷=Si, C, Ge or Sn, X ¹=C _1-4Alkyl or phenyl, X ²=Cl, BH ₄, H, C _1-4Alkyl, H[(CH ₃) ₃Si] ₂, CH[(CH ₃) ₃Si] ₂, CH ₂[(CH ₃) ₃Si] or tetrahydrofuran (THF) (THF) base, M=lanthanon, yttrium or scandium, L=(CH ₃) ₃Si, Li (THF) ₄, [Y-crown ether] or [Y-crown ether]-2,4-epoxy six ring, n=1 or 0, m=1 or 2, when m=2, n=0, Y=monovalence metal, crown ether=hexaoxacyclooctadecane-6-6 or 15-crown ether-5.Perhaps: R ¹, R ², R ³, R ⁴, R ⁵, R ⁶Be H, R ⁷Be C, X ¹Be phenyl, X ²Be Cl, M=lanthanon, yttrium or scandium, L=ClLi (THF) ₄, n=1, m=1; Perhaps: R ¹, R ², R ³, R ⁴, R ⁵, R ⁶Be H, R ⁷Be C, X ¹Be phenyl, X ²Be BH ₄, M=lanthanon, yttrium or scandium, L=BH ₄Li (THF) ₄, n=1, m=1; Perhaps: R ¹, R ², R ³, R ⁴, R ⁵, R ⁶Be H, R ⁷Be C, X ¹Be phenyl, X ²Be THF _n, M=lanthanon, yttrium or scandium, n=0, m=1;

Title complex of the present invention also can be represented with this structural formula of phase:

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, X ¹, X ², L, n and m as mentioned above.Dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding of the present invention can be

Deng,

Wherein Ph=phenyl, the t-Bu=tertiary butyl, E=CH or N, THF=tetrahydrofuran (THF).

Behind part dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding recrystallization, carry out the analysis of X-ray single crystal diffraction and confirmed their structure than simple molecules.

With title complex { [(CH ₃) ₂Si (C ₅H ₅) (C ₁₃H ₈)] [YCl] ₂{ [Ph ₂Si (t-Bu-C ₅H ₃) (C ₁₃H ₈)] [YCl] ₂Low temperature recrystallization in toluene obtains two Cs and C ₁Symmetric silyl-bridged fluorenyl ring penta 2 rare title complexs 1 and 5 monocrystalline.Its main crystallographic data is listed in table 1, and main bond distance, bond angle are listed in the table 2, and they have the denominator of metal bridge di-aggressiveness, and crystalline structure as depicted in figs. 1 and 2.

The crystallographic data of table 1 title complex 1,5

Title complex 15

Molecular formula C ₅₄H ₅₂Si ₂Cl ₂Y ₂C ₇₄H ₆₆Si ₂Cl ₂Y ₂

Molecular weight 1005.89 1260.22

Crystal formation three oblique monocline

Color is yellow

T(K) 293 293

a() 11.669(2) 25.996(4)

b() 11.947(3) 10.008(2)

c() 9.286(2) 24.261(3)

α(°) 100.91(2) -

β(°) 100.00(1) 96.27(1)

γ(°) 72.22(2) -

V(A ³) 1201.2(5) 6274(1)

Z 1 4

Spacer P-1 C2/c

D/g?cm ^-3 1.390 1.334

The accurate factor 0.064 0.065

The main bond distance and the bond angle of table 2 title complex 1,5

Title complex 15

Y-Y’ 3.797(8) 3.659(1)

Y-Cl 2.649(2) 2.633(2)

Y-Cl’ 2.638(2) 2.648(4)

Y-C(1) 2.601(6) 2.604(6)

Y-C(2) 2.580(8) 2.645(6)

Y-C(3) 2.599(8) 2.702(6)

Y-C(4) 2.623(7) 2.645(6)

Y-C(5) 2.635(5) 2.648(5)

Y-C(7) 2.681(6) 2.632(6)

Y-C(8) 2.699(6) 2.732(6)

Y-C(9) 2.651(6) 2.825(6)

Y-C(10) 2.599(6) 2.745(5)

Bond angle (°)

Y-Cl-Y” 91.82(6) 88.0(1)

Cl-Y-Cl’ 88.18(6) 102.4(3)

Y-C(3)-C(31) - 128.0(4)

Y-C(3)-H(3) 124.4(4) -

C(5)-Si-C(6) 118.1(2) 116.1(2)

C(19)-Si-C(25) - 106.9(3)

C(20)-Si-C(19) 107.9(4) -

With title complex [Ph ₂C (C ₅H ₄) (C ₁₃H ₈) LuCl ₂] [Li (THF) ₄] 7 in THF/ normal hexane mixed solvent recrystallization, obtained the muriatic red crystals of phenylbenzene methylene-bridged fluorenyl cyclopentadiene base lutetium.Its ionic compound of forming by the ion pair that is separated from each other of X-ray single crystal diffraction analytical proof.Its molecular structure as shown in Figure 3.Main crystallographic data and main bond distance, bond angle are listed in respectively in table 3 and 4.Its anionicsite is taked the tetrahedral bridged combined metal structure of class.This containing (Cp) ₂LnX ₂ ^-It is less that the rare earth compounding of anion structure is reported in the literature.The distance of carbon atom is similar substantially to the metal carbon bond distance in other rare earth metallocene compound on metal and the luxuriant ring, and is shorter than metal carbon bond far away apart from the metal carbon bond that bridge atom carbon is nearer.The central metal in this class formation and the bond distance of chlorion are generally shorter, and the bond angle of respective metal and two chlorine atoms is bigger.

The cationic moiety of title complex 7 [Li (THF) ₄] ⁺Be same as positively charged ion in the ionic title complex.Lithium atom and four tetrahydrofuran (THF) coordinations form tetrahedral structure.The bond distance of lithia key is in the scope of 1.907 (9)-1.934 (9) A.

The crystallographic data of table 3 title complex 7

Molecular formula molecular weight color crystal formation spacer A, () B, () c, ()

C ₄₇H ₅₄Cl ₂LiO ₄Lu 935.76 red three oblique P-1, (#2) 12.529, (5) 15.280, (3) 12.247, (3)

α(°) β(°) γ(°) V(A ³) F000 D _calcg/cm ³T(k) μ _(Mo-Kα)(cm-1)

99.06(2) 100.53(2) 76.02(2) 2173(1) 952.00 293 1.430 24.35

The main bond distance (A) of table 4 title complex 7 and bond angle (°)

Bond distance () bond angle (°)

Lu-Cl(1) 2.496(2) Cl(1)-L7-Cl(2) 96.48(7)

Lu-Cl(2) 2.501(2) Cl(1)-Lu-C(13) 126.3(1)

Lu-C(1) 2.631(5) Cl(2)-Lu-C(13) 124.8(1)

Lu-C(6) 2.818(5) Cl(1)-Lu-C(15) 126.6(1)

Lu-C(7) 2.841(5) Cl(2)-Lu-C(15) 126.7(1)

Lu-C(12) 2.673(6) C(1)-C(13)-C(14) 126.4(4)

Lu-C(13) 2.570(6) C(12)-C(13)-C(14) 125.8(4)

Lu-C(15) 2.561(5) C(13)-C(14)-C(15) 101.7(4)

Lu-C(16) 2.567(5) C(14)-C(15)-C(16) 124.9(4)

Lu-C(17) 2.615(5) C(14)-C(15)-C(19) 124.3(4)

Lu-C(18) 2.626(5) C(20)-C(14)-C(26) 103.5(4)

Lu-C(19) 2.577(5)

Dialkyl methylene-bridged fluorenyl cyclopentadiene base hydroborate (C ₁₃H ₈) CPh ₂(C ₅H ₄) La (BH ₄) ₂Li (THF) ₄9 and (C ₁₃H ₈) CPh ₂(C ₅H ₄) Nd (BH ₄) ₂Li (THF) ₄10 also belong to the anionic structure.Anionicsite is by π-part, rare earth ion and bimolecular BH ₄Part is formed; Positively charged ion also is made up of lithium ion of tetramolecular THF complexing.Have two remarkable structural feature: promptly big B-M-B ' angle and short M-B key, with the identical crystalline structure of title complex 10 tools.The crystallographic data of coordination thing 10 and bond distance's bond angle are listed in respectively in table 5 and 6, and molecular structure is listed among Fig. 4.

The crystallographic data of table 5 title complex 9,10

Title complex 9 10

Molecular formula C ₄₇H ₆₂B ₂LaO ₄Li C ₄₇H ₆₂B ₂NdO ₄Li

Molecular weight 858.47 863.81

Color is red

2θmax(°) 26.3 26.2

Crystal formation Triclinic Triclinic

Spacer P-1 (#2) P-1 (#2)

a() 12.422(3) 12.415(6)

b() 16.343(4) 16.245(5)

c() 12.337(4) 12.337(5)

α(°) 110.50(2) 110.43(3)

β(°) 103.16(2) 103.23(4)

γ(°) 76.16(2) 76.13(3)

V(A ³) 2249(1) 2234(1)

T (K) temperature 293 293

Z 2 2

For its anionicsite { (C ₁₃H ₈) CPh ₂(C ₅H ₄) Nd (BH ₄) ₂} ^-, the central metal neodymium ion is with η ³-pattern and fluorenes ring and luxuriant ring coordination, and connecting two BH again symmetrically ₄ ^-Ion, whole anionicsite is negative monovalence.Central metal neodymium and two boron atom angulation ∠ B1-Nd-B2 (99.3 (2) °); The bond distance of two Nd-B keys is shorter, obviously has the feature of tridentate ligand.BH ₄Part is that the pattern with tridentate ligand exists in this title complex.

The major key of table 6 title complex 9,10 long (A) and bond angle (°)

Title complex 9 (La) 10 (Nd)

Ln-B(1) 2.717(5) 2.642(7)

Ln-B(2) 2.713(5) 2.658(6)

Ln-H(23) 2.37(6) 2.53(4)

Ln-H(24) 2.43(4) 2.38(6)

Ln-H(25) 2.38(5) 2.38(4)

Ln-H(27) 2.52(5) 2.39(4)

Ln-H(28) 2.49(5) 2.45(5)

Ln-H(29) 2.40(4) 2.45(5)

Ln-C(1) 2.845(3) 2.793(4)

Ln-C(6) 3.001(3) 2.946(4)

Ln-C(7) 3.010(3) 2.954(4)

Ln-C(12) 2.861(3) 2.806(4)

Ln-C(13) 2.788(3) 2.725(4)

Ln-C(15) 2.763(3) 2.701(4)

Ln-C(16) 2.769(3) 2.699(4)

Ln-C(17) 2.828(4) 2.771(4)

Ln-C(18) 2.830(4) 2.767(4)

Ln-C(19) 2.769(3) 2.708(4)

B(1)-H(23) 0.98(6) 1.05(5)

B(1)-H(24) 1.07(5) 0.97(5)

B(1)-H(25) 1.14(5) 1.05(5)

B(1)-H(26) 1.16(4) 1.04(6)

B(2)-H(27) 1.03(5) 1.09(5)

B(2)-H(28) 0.98(5) 1.05(6)

B(2)-H(29) 1.13(4) 0.99(5)

B(2)-H(30) 1.06(5) 1.10(5)

B(1)-Ln-B(2) 99.5(2) 99.3(2)

C(1)-C(13)-C(14) 126.6(3) 126.8(3)

C(12)-C(13)-C(14) 125.6(3) 125.3(3)

C(13)-C(14)-C(15) 102.1(2) 102.4(3)

C(14)-C(15)-C(16) 125.9(3) 125.5(3)

C(14)-C(15)-C(19) 125.8(3) 125.9(4)

C(20)-C(14)-C(26) 102.7(2) 103.1(3)

On the carbocyclic ring distance of carbon atom from bridge carbon begin ever-increasing phenomenon also with two big BH ₄Non-bonded interaction between the part is relevant.The carbon on the near more luxuriant ring of end of the bridge carbon and the distance of metal are short more.

The feature structure of phenylbenzene methylene-bridged fluorenyl cyclopentadiene base rare earth hydroborate is metal and BH ₄The special coordination mode of part.Two BH ₄Part almost completely symmetrically with central metal Cheng Jian.Each BH ₄With central metallic ions is to pass through μ ₃-type hydrogen atom bridge links together boron atom and atoms metal.Title complex 7,9 and 10 be by two mutually independently yin, yang be dimerous, equal typical η of tool ³-coordination feature.

Dual anion type phenylbenzene methylene-bridged fluorenyl cyclopentadiene base rare earth hydroborate [K (hexaoxacyclooctadecane-6-6) { (C with unique novel texture feature ₁₃H ₈) CPh ₂(C ₅H ₄) Nd (Bh ₄) ₂] ₂(C ₄H ₈O ₂) in 11, it no longer is tetrahydrofuran (THF) or ether etc. that neutral is given the electronics part, but encircle 18 hat 6 ethers and 1,4-epoxy six alkane greatly.This dianion rare earth hydroborate 11 is made up of three separate parts.The molecular structure of title complex 11 is seen Fig. 5.Main crystallographic data and relevant bond distance's bond angle are listed in respectively in table 7 and 8.

Title complex 11 has a negatively charged ion macoradical { (C ₁₃H ₈) CPh ₂(C ₅H ₄)-Nd (BH ₄) ₂} ^-, and by the positively charged ion macoradical { [K (18-crown-6)] with two positive charges ₂[C ₄H ₈O ₂] ²⁺Separate.[K (18-crown-6)] ⁺Be by 1,4-epoxy six alkane C ₄H ₈O ₂Two Sauerstoffatoms be formed by connecting as a whole with a potassium atom respectively.The structure of the anionicsite of title complex 11 and 9,10 similar, but because the one-piece construction difference of title complex also has evident difference between them.Its anionicsite { (C ₁₃H ₈) CPh ₂(C ₅H ₄)-Nd (BH ₄) ₂} ^-In the central metal neodymium also be with η ³-pattern and fluorenes ring and luxuriant ring coordination, and connecting two BH again symmetrically ₄ ^-Ion.

The main crystallographic data of table 7 title complex 11

Molecular formula C ₄₇H ₅₈NdB ₂KO ₇B () 20.217 (2)

Molecular weight 915.91 c () 14.106 (1)

Crystal form M onoclinic β (°) 92.60 (1)

Spacer P2 ₁/ a V (A ³) 4424.0 (9)

A () 15.530 (3) colors are red

Metal center is also caused by the big steric hindrance of fluorenyl than long to the distance of fluorenes ring, and the bond distance of carbon atom begins ever-increasing from bridge carbon on metal and the fluorenes ring.The carbon on the near more luxuriant ring of end of the bridge carbon and the distance of metal are short more.Two BH ₄Part also be symmetrically with central metal Cheng Jian.Each BH ₄With central metallic ions also is by μ 3-type hydrogen atom bridge boron atom and atoms metal to be linked together.The feature that also obviously has tridentate ligand of two Nd-B keys, two Nd-B-H _tThe bond angle that is become also almost is in line.In the title complex 11, two potassium ions not only with 18 hats 6 on six Sauerstoffatoms be in key, and respectively with one 1, a Sauerstoffatom in the 4-dioxane molecule links to each other, and promptly forms { [K (18-crown-6)] [C ₄H ₈O ₂] [K (18-crown-6)] ²⁺Structure, it makes whole cationic moiety become as a whole.Because two anionic groups are listed in the both sides of this cation group respectively, and whole molecule is made up of three separate parts.

The main bond distance () of table 8 title complex 11 and bond angle (°)

K-O(1) 2.754(6) B(1)-H(23) 0.97 Nd-B(2) 2.623(7)

K-O(2) 2.805(6) B(1)-H(24) 1.20 Nd-B(23) 2.47

K-O(3) 2.740(5) B(1)-H(25) 1.20 Nd-B(24) 2.40

K-O(4) 2.696(5) B(1)-H(26) 1.15 Nd-B(25) 2.41

K-O(5) 2.881(5) B(2)-H(27) 1.07 Nd-B(27) 2.48

K-O(6) 2.757(6) B(2)-H(28) 1.22 Nd-B(28) 2.39

K-O(7) 2.78(1) B(2)-H(29) 1.03 Nd-B(29) 2.52

K-C(3) 3.403(7) B(2)-H(30) 1.07 Nd-C(1) 2.817(5)

K-C(4) 3.322(7) Nd-B(1) 2.641(8) Nd-C(6) 2.938(6)

Nd-C(7) 2.915(6) Nd-C(15) 2.701(5) Nd-C(19) 2.718(5)

Nd-C(12) 2.781(5) Nd-C(16) 2.691(5) Nd-C(18) 2.753(6)

Nd-C(13) 2.752(5) Nd-C(17) 2.741(6)

B(1)-Nd-B(2) 100.2(3) C(1)-C(13)-C(14) 126.7(5)

C(12)-C(13)-C(14) 126.0(5) C(14)-C(15)-C(16) 126.0(5)

C(13)-C(14)-C(15) 103.1(4) C(14)-C(15)-C(19) 125.0(5)

C(20)-C(14)-C(26) 102.3(4) Nd-B(1)-H(26) 177.1

Nd-B(2)-H(30) 171.5

The structure of rare earth hydroborate 11 mainly is because the coordination environment around the potassium metal ion is different fully during with respect to complexing four molecule tetrahydrofuran (THF)s with 9 and 10 textural difference.Macrocyclic crown ether 18 hat 6 becomes two dimensional structure with the potassium ion complexing, but potassium ion coordination space on every side is also bigger, can be further and π-part coordination Cheng Jian, and make title complex more stable; And four molecule tetrahydrofuran (THF)s and alkalimetal ion complexing are generally tetrahedral structure, do not allow on the space alkalimetal ion again with other part coordination.Therefore, be isolated mutually between the yin, yang ion in title complex 9 and 10 the structure, by electrostatic attraction they are linked together; But in title complex 11, but be not isolated fully between the yin, yang ion, the weak key effect that is in that exists between them makes that three relatively independent parts organically are linked to be an integral body in the molecule.

In toluene-normal hexane mixed solvent, cultivate and obtained title complex [(CH ₃) ₂Si (C ₅H ₄) (C ₁₃H ₈)]-DyCH (TMS) ₂14, [(CH ₃) ₂Si (C ₅H ₄) (C ₁₃H ₈)] ErCH (TMS) ₂15, [(CH ₃) ₂Si (C ₅H ₄)-(C ₁₃H ₈)] DyN (TMS) ₂16, [(CH ₃) ₂Si (C ₅H ₄) (C ₁₃H ₈)] ErN (TMS) ₂17 and [Ph ₂C (C ₅H ₄)-(C ₁₃H ₈) LuN (TMS) ₂] crystal analyzed of 18 suitable X-ray single crystal diffraction, and measured its crystalline structure, shown in Fig. 6,7 and 8, above-mentioned alkylate still is that the amido title complex does not all have the solvent complex molecule.Compound 14,16 and 17 main bond distance join bond angle and list in the table 9,10 and 11.

Main bond distance () bond angle of table 9 title complex 14 (°)

The bond distance

Dy-C(27) 2.364(9) Dy-Si(2) 3.148(3)

Dy-C(21) 2.756(10) Dy-C(1) 2.589(10)

Dy-C(2) 2.66(1) Dy-C(3) 2.69(1)

Dy-C(4) 2.619(10) Dy-C(5) 2.604(9)

Dy-C(6) 2.592(8) Dy-C(7) 2.662(8)

Dy-C(8) 2.816(8) Dy-C(9) 2.830(9)

Dy-C(10) 2.666(8) Si(2)-C(21) 1.898(10)

Si(2)-C(27) 1.818(9) Si(3)-C(27) 1.840(8)

Si(3)-C(26) 1.88(2)

Bond angle

Dy-C(27)-H(37) 100.2(9) Dy-C(27)-Si(2) 96.8(5)

Dy-C(27)-Si(3) 129.8(5) C(5)-Si(1)-C(9) 99.8(4)

C(10)-Si(1)-C(20) 108.2(5) C(2)-Dy-C(27) 102.8(4)

C(3)-Dy-C(27) 93.7(3) Si(2)-C(27)-Si(3) 123.5(5)

Dimethyl bridged fluorenyl cyclopentadiene base rare earth alkyl complexes 14 belongs to typical Cp ' ₂M-X class rare earth compounding.With other with [(CH (TMS) ₂] crystalline structure of coordinate organic RE metallocene complex is similar, variation has taken place in five carboatomic rings on the fluorenyl and the coordination mode of metal, and fluorenes ring and center rare earth ion in the title complex 14 have tangible η ³-coordination feature, and luxuriant ring and rare earth ion are still typical η ⁵-pattern, with the similar of amido title complex 16, the less end of the bridge angle in the alkyl complexes 14 obviously strengthens the tension force on the Siliciumatom end of the bridge, forces metal distance of carbon atom to π-ring obviously elongated; Central metallic ions and alkyl CH (TMS) ₂On α-C distance very short, it is a shortest class in present known terminal σ-rare earth carbon bond.This big coordination space with title complex 14 is relevant; In addition, this constitutional features is relevant with the symmetry of title complex.Usually can judge α-CH by the angle between the M-C-H ... Ln agostic interacts.The angle of ∠ Dy-C27-H37 in the title complex 14 is 100.29 °, and the bond distance of Dy-H37 key (2.71 ) and C27-H37 key (0.972 ) do not have elongated phenomenon, infers not have α-CH ... Lnagostic interacts.

The main bond distance () of table 10 title complex 16,17 and bond angle (°)

Title complex 16 17

Bond distance ()

Ln-N 2.207(5) 2.194(4)

Ln-C(21) 3.569(8) 3.667(7)

Ln-C(26) 2.901(8) 2.834(5)

Ln-Si(1) 3.407(2) 3.382(2)

LnSi(2) 3.469(2) 3.504(2)

LnSi(3) 3.152(2) 3.106(2)

Si(3)-C(26) 1.899(7) 1.896(5)

Si(3)-N 1.701(6) 1.697(4)

Si(2)-C(21) 1.861(9) 1.868(7)

Si(2)-N 1.699(5) 1.705(4)

Ln-C(1) 2.630(7) 2.596(6)

Ln-C(2) 2.657(8) 2.652(6)

Ln-C(3) 2.657(7) 2.647(5)

Ln-C(4) 2.615(7) 2.599(5)

Ln-C(5) 2.633(7) 2.603(4)

Ln-C(6) 2.618(6) 2.604(5)

Ln-C(7) 2.712(6) 2.670(5)

Ln-C(8) 2.843(6) 2.815(5)

Ln-C(9) 2.829(7) 2.816(5)

Ln-C(10) 2.675(6) 2.685(5)

Bond angle (°)

Si(2)-N-Si(3) 128.3(3) 127.1(2)

Ln-N-Si(3) 106.8(2) 105.2(2)

Ln-N-Si(2) 124.8(3) 127.6(2)

C(5)-Si(1)-C(6) 99.7(3) 99.5(2)

C(19)-Si(1)-C(20) 107.8(4) 107.7(3)

N-Ln-C(2) 93.0(2) 90.9(2)

N-Ln-C(3) 98.7(2) 98.2(2)

Cultivate the monocrystalline that has obtained title complex 18 in tetrahydrofuran (THF)-normal hexane mixed solvent, analyze by X-ray single crystal diffraction, measured its molecular structure, as shown in the figure, main bond distance's bond angle is listed among the table 4-10.

Compare with the structure of corresponding phenylbenzene methylene-bridged fluorenyl cyclopentadiene base rare earth chloride, the amido title complex of this type of part no longer is an ionic structure, but the neutral compound of a solvent-free complexing.Therefore in the also difference slightly in form of metal and two π-part Cheng Jian.The distance of the carbon atom on Lu to two π of center rare earth metal-ring part obviously shortens than its muriate.Sterically hindered being eased around the metal ion, metal strengthens with the key effect that becomes of π-ring part.

The main bond distance () of table 11 title complex 18 and bond angle (°)

Bond distance ()

Lu-C(32) 2.74(1) Lu-C(7) 2.558(9)

Lu-N 2.167(8) Lu-C(8) 2.568(10)

Lu-Si(1) 3.020(3) Lu-C(13) 2.741(9)

Si(2)-N 1.722(9) Lu-C(15) 2.541(10)

Si(1)-N 1.687(10) Lu-C(16) 2.533(9)

Si(1)-C(32) 1.89(1) Lu-C(17) 2.59(1)

Si(2)-C(37) 1.87(2) Lu-C(18) 2.58(1)

Lu-C(1) 2.731(10) Lu-C(19) 2.588(9)

Lu-C(6) 2.621(9)

Bond angle (°)

Lu-N-Si(11) 102.5 C(20)-C(14)-C(26) 103.2(8)

Lu-N-Si(2) 131.9(5) C(17)-Lu-N 93.3(4)

Si(2)-N-Si(1) 125.6(5) C(18)-Lu-N 103.1(4)

C(7)-C(14)-C(15)?101.1(7)

Metal nitrogen key bond distance in the title complex 18 of carbon atom bridging (Lu-N=2.167 (8) ) is basic identical with the metal nitrogen key in the silyl-bridged title complex.

Title complex 14,16,17 and 18 crystallographic data are listed in the table 11.

Table 12 title complex 14,16,17 and 18 crystallographic data

Title complex 14 16 17 18

Molecular formula C ₂₇H ₃₇Si ₃Dy C ₁₆H ₃₆Si ₃Ndy C ₂₆H ₃₆Si ₃Ner C ₃₇H ₄₀Si ₂Nlu

Molecular weight 608.35 609.33 614.09 729.87

Crystal formation monocline monocline monocline three is oblique

Color is yellow yellow red

a() 13.759(2) 9.123(1) 9.097(4) 15.777(3)

b() 9.077(9) 11.843(9) 11.759(4) 17.147(6)

c() 45.18(1) 25.522(4) 25.664(5) 14.434(5)

α(°) - - - 110.10(3)

β(°) 91.06(2) 93.47(1) 93.41(3) 93.46(2)

γ(°) - - - 91.39(2)

V(A ³) 5642(1) 2752.4(6) 2740(1) 3656(1)

Z 8 4 4 4

Spacer P2 ₁/ n P2 ₁/ n P2 ₁/ n P-1

D/g?cm ^-3 1.432 1.470 1.488 1.326

The accurate factor 0.052; 0.066 0.034; 0.053 0.030; 0.039 0.057; 0.073

No matter rare earth compounding for the silica-based bridging of dimethyl is alkylide 14, or aminated thing 16,17, and they all belong to oblique system, P2 ₁/ n spacer; And the rare earth amido title complex 18 of carbon bridging belongs to triclinic(crystalline)system, the P-1 spacer.

In the molecular structure of these title complexs, no matter be alkyl or amido part, can observe one of them trimethyl silicon based substituting group and central metallic ions has less angle, and has significantly interaction between β-Si-Me key and the center rare earth ion.

Table 12 has been enumerated in title complex 14,16,17 and 18 and β-Si-Me to table 15 ... bond distance and bond angle data that Ln agostic interaction is relevant, presentation of results mainly are that β-Si-C key and central metal interact in these title complexs, rather than γ-C-H.

In table 13 title complex 14 with " agostic " the relevant chemical bond bond distance () that interacts

Chemical bond bond distance () chemical bond bond distance () chemical bond bond distance ()

Dy-C ₂₇ 2.364(9) Dy-H ₂₁ 2.50 Si ₂-C ₂₂?1.87(1)

Dy-Si ₂ 3.148(3) C ₂₇-H ₃₇?0.972 Si ₂-C ₂₃?1.86(1)

Dy-C ₂₁ 2.756(10) C ₂₁-H ₁₉?0.966 Si ₂-C ₂₇?1.818(9)

Dy-H ₃₇ 2.71 C ₂₁-H ₂₁?0.965 Si ₃-C ₂₇?1.840(8)

Dy-H ₁₉ 2.50 C ₂₁-H ₂₀?0.950

Dy-H ₂₀ 3.68 Si ₂-C ₂₁?1.90(1)

In table 14 title complex 16,17 with " agostic " the relevant chemical bond bond distance () that interacts

Chemical bond 16 17 chemical bonds 16 17

Ln-N 2.207(5) 2.194(4) Si ₂-C ₂₁ 1.861(9) 1.868(7)

Ln-Si ₃ 3.152(2) 3.106(2) Si ₂-C ₂₂ 1.878(10) 1.864(7)

Ln-C ₂₆ 2.901(8) 2.834(5) Si ₂-C ₂₃ 1.862(8) 1.869(7)

Ln-H ₃₅ 2.72 2.60 C ₂₆-H ₃₄ 0.99 0.953

Ln-H ₃₆ 2.71 2.61 C ₂₆-H ₃₅ 0.94 0.947

Ln-H ₃₇ 3.88 3.78 C ₂₆-H ₃₆ 0.96 0.950

Si ₃-C ₂₆?1.899(7) 1.896(5) N-Si ₂ 1.699(5) 1.705(4)

Si ₃-C ₂₄?1.850(8) 1.864(6) N-Si ₃ 1.701(6) 1.697(4)

Si ₃-C ₂₅?1.862(8) 1.862(7)

In table 15 title complex 18 with " agostic " the relevant chemical bond bond distance () that interacts

Lu ₁-N ₁ 2.167(8) N ₁-Si ₁?1.867(10) C ₃₂-H ₂₃?0.97

Lu ₁-C ₂ 2.74(1) N ₁-Si ₂?1.722(9) C ₃₂-H ₂₄?0.96

Lu ₁-H ₂₃?2.50 Si ₂-C ₃₅?1.85(2) C ₃₂-H ₂₅?0.94

Lu ₁-H ₂₄?2.50 Si ₂-H ₃₆?1.86(2)

Lu ₁-H ₂₅?3.50 Si ₂-C ₃₇?1.87(2)

Title complex 14,16 and 18 X-ray single crystal diffraction analysis revealed amido title complex and alkyl complexes all are neutral.Central metallic ions and two π-parts are common chelate structure.Fluorenes ring and central metal ion coordination mode are η ⁵-feature.All there is the intramolecularly that makes title complex more stable in they under solid-state ^βSi-Me ... Ln agostic interacts.

Dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding of the present invention can be synthetic respectively by following method:

With molecular formula is (X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶) Y ₂Univalent metal salt and equimolar MCl ₃Or M (BH ₄) ₃(THF) ₃To room temperature, react 1-50h for-78 ℃ in the neutralization of tetrachloro furans solvent, generate { [(X ¹) ₂(R ²) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶)] [MCl] _n, (X ¹) ₂(R ²) (C ₅R ¹R ²R ³R ⁴) M (μ ₂-Cl) ₂Li-(THF) ₄Or rare earth hydroborate (X with dication type structure ¹) ₂(R ²) (C ₅R ¹R ²R ³R ⁴)-M (BH ₄) ₂Li (THF) ₄

With molecular formula is (X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶) Y ₂, M (BH ₄) ₃(THF) ₃, hexaoxacyclooctadecane-6-6 or 15-crown ether-5 mol ratio be 1: 1: during 1-100, in organic solvent ,-78 ℃ are reacted 1-5h to room temperature, do not have 2, during the 4-dioxane, generate [Y18-crown ether-6 or 15-crown ether-5] { (X ¹) ₂R ⁷(C ₅R ¹R ²R ³R ⁴)-M (C ₁₃H ₆R ⁵R ⁶) M (BH ₄) ₂.Contain 2 in the reaction, during the 4-dioxane, generate { (X ¹) ₂R ⁷(C ₅R ¹R ²R ³R ⁴) M (C ₁₃H ₆R ⁵R ⁶) M (BH ₄) ₂} ₂[C ₄H ₈O ₂], the latter reaction recommends mol ratio to be followed successively by 1: 1: 1-100: during 1-100.2, the 4-dioxane also can be the compound that exists in the crown ether.

With molecular formula is (X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶) Y ₂To room temperature, react 10-50h at-78 ℃ with equimolar two calcium iodides or ytterbium, generate (X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶)-Sm or Yb-(THF) _m

MCl in organic solvent ₃With equimolar YCH (TMS) ₂Or YN (TMS) ₂,, generate (X at-78 ℃ to 60 ℃ reaction 10-80h ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶) MCH (TMS) ₂Or (X ¹) ₂(R ⁷)-(C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶) MN (TMS) ₂

With X ¹ ₂R ⁷(C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶) M (μ ₂-Cl) ₂Y (THF) ₄With equimolar M ¹N (TMS) ₂To room temperature, react 20-50h for-78 ℃ in the organic solvent neutralization, generate [X ¹ ₂R ⁷(C ₅R ¹R ²R ³R ⁴)-(C ₁₃H ₆R ⁵R ⁶)] MN (TMS) ₂

R in the above-mentioned reaction ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, X ¹, X ², L, n, m, THF and Y be like preceding described, TMS=is trimethyl silicon based.

Adopt aforesaid method synthetic title complex, can be in solvent recrystallization, be particularly suited in the mixed solvent of polarity and non-level property, carrying out recrystallization.Recrystallization is appropriate to the occasion at low temperatures for well.

Dialkyl methylene-bridged fluorenyl cyclopentadiene base alkene soil title complex of the present invention can be used for the catalyzer of polyreaction, but catalysis methyl methacrylate polyreaction, catalysis third rare fat polymerization etc.As Polymerization of Methyl is all shown higher initiating activity, reach 60-100%, wait until the methyl esters (rr=55-83%) of syndiotactic polymethyl acid preferably in can obtaining.This polyreaction can be carried out in wide temperature range, and resulting polymers has higher molecular weight (Mn＞10 ⁵) and narrower molecular weight distribution (MW/Mn=1.215).Polymerization that also can medium transformation efficiency 40-60% ground catalyzing propone nitrile.

Description of drawings

Fig. 1 is title complex { [(CH ₃) ₂Si (C ₅H ₅) (C ₁₃H ₈)] [YCl] ₂1 crystalline structure

Fig. 2 is title complex { [Ph ₂Si (t-Bu-C ₅H ₃) (C ₁₃H ₈)] [YCl] ₂5 crystalline structure

Fig. 3 is title complex [Ph ₂C (C ₅H ₄) (C ₁₃H ₈)] LuCl ₂] [Li (THF) ₄] 7 crystalline structure

Fig. 4 is the negatively charged ion [Ph of title complex 10 ₂C (C ₅H ₄) (C ₁₃H ₈) Nd] Nd (BH ₄) ₂] crystalline structure

Fig. 5 is title complex [K (hexaoxacyclooctadecane-6-6) { (C ₁₃H ₈) CPh ₂(C ₅H ₄) Nd (BH ₄) ₂] ₂[C ₄H ₈O ₂] 11 crystalline structure

Fig. 6 is title complex [(CH ₃) ₂Si (C ₅H ₄) (C ₁₃H ₈)] DyCH (TMS) ₂14 crystalline structure

Fig. 7 is title complex [(CH ₃) ₂Si (C ₅H ₄) (C ₁₃H ₈)] DyN (TMS) ₂16 crystalline structure

Fig. 8 is title complex [Ph ₂C (C ₅H ₄) (C ₁₃H ₈)] LuN (TMS) ₂] 18 crystalline structure

It is anti-that dialkyl methylene-bridged fluorenyl cyclopentadiene base alkene soil complex of the present invention can not only be used for polymerization The catalyst of answering, and simple synthetic method are expected to commercial Application.

The present invention will be helped further to understand by following embodiment, but content of the present invention can not be placed restrictions on.

Embodiment 1

1. the silica-based bridged fluorenyl cyclopentadiene base of dimethyl Yttrium trichloride { [Me ₂Si (C ₅H ₄) (C ₁₃H ₈)] [YCl] ₂(1) preparation

The silica-based bridged fluorenyl cyclopentadiene ylidene ligands of 1.83g (6.3mmol) dimethyl is dissolved in the ether of 100ml, slowly drips the hexane solution of the n-Butyl Lithium of 7.7ml (1.65M) under the frozen water cooling, solution becomes redness by yellow, room temperature reaction 5 hours.Then the diethyl ether solution of resulting part dilithium salt slowly is added drop-wise to and is cooled to-78 ℃ and is suspended with 1.24g (6.36mmol) YCl ₃The 20ml ether in, slowly be warming up to stirring at room reaction two days.The centrifugation precipitation shifts clear liquid.Vacuum is drained solvent, and the gained solid product shifts extracting solution with the methylbenzene extraction of 50ml, and slowly concentrated solvent places-20 ℃ of coolings to separate out xanchromatic crystal 0.56g (21.4%), m.p.:＞320 ℃ to 20ml under vacuum.Ultimate analysis: C ₅₄H ₂₂Si ₂Cl ₂Y ₂(1): calculated value C, 61.84; H, 4.83. measured value: C, 62.12; H, and 4.92%.MS (EI) (70 eV 50-400 ℃): m/z821 (5.54, [M] ⁺), 663 (3.64, [M-YCl ₂] ⁺), 497 (12.35, [M-YCl ₂-C ₁₃H ₉] ⁺), 409 (100, [M/2] ⁺), 374 (40.25, [M/2-Cl] ⁺). ¹H NMR (300MHz, C ₆H ₆-D ₆): δ=8.06 (3,2H, Flu, J=8.4Hz), 7.89 (d, 2H, Flu, J=8.5Hz), 7.30 (m, 4H, Flu), 6.18 (m, 2H, Cp), 5.80 (m, 2H, Cp), 0.52 (s, 6H, SiMe ₂) .FT-Raman (cm ^-1): 3067 (m), 1527 (s), 1437 (s), 1336 (vs), 1209 (s), 1004 (m), 740 (m), 660 (m), 521 (w).

2. the silica-based bridged fluorenyl cyclopentadiene base of dimethyl lutecium chloride { [Me ₂Si (C ₅H ₄) (C ₁₃H ₈)] [LuCl] ₂(2) preparation

Experimental procedure is with the preparation of title complex 1.With 1.28g (4.54mmol) LuCl ₃Dilithium salt reaction with the part of equimolar amount obtains xanchromatic crystal 0.35g (15.6%), m.p:220-222 ℃.Ultimate analysis: C ₅₄H ₂₂Si ₂Cl ₂Lu ₂(2): calculated value C, 46.37; H, 3.48. measured value: C, 46.19; H, and 3.74%MS (EI) (70eV, 50-400 ℃): m/z993 (16.71, [M] ⁺), 749 (2.21, [M-YCl ₂] ⁺), 583 (4.65, [M-YCl ₂-C ₁₃H ₉] ⁺), 496 (100, [m/2] ⁺, 461 (32.66, [M/2-Cl] ⁺). ¹H NMR (300MHz, C ₆H ₆-D ₆): δ=8.04 (d, 2H, Flu, J=8.3Hz), 7.89 (d, 2H, Flu, J=8.6Hz), 7.27 (m, 2H, Flu), 7.16 (m, 2H, Flu), 6.06 (t, 2H, Cp, J=2.6Hz), 5.67 (t, 2H, Cp, J=2.6Hz), 0.54 (s, 6H, SiMe ₂) .FT-Raman (cm ^-1): 3069 (m), 1520 (s), 1438 (s), 1337 (vs), 1209 (s), 1170 (m), 740 (m), 660 (m), 521 (w), 419 (m), 292 (m).

3. the silica-based bridged fluorenyl cyclopentadiene base of dimethyl Erbium trichloride { [Me ₂Si (C ₅H ₄) (C ₁₃H ₈)] [ErCl] ₂(3) preparation

Experimental procedure is with the preparation of title complex 1.With 1.47g (5.35mmol) ErCl ₃Dilithium salt reaction with the part of equimolar amount obtains xanchromatic crystal 0.5g (19.2%), m.p:＞320 ℃.Ultimate analysis: C ₅₄H ₂₂Si ₂Cl ₂Er ₂(3): calculated value C, 52.26; H, 4.11. measured value: C, 52.35; H, and 4.22%.MS (EI) (70eV, 50-400 ℃): m/z981 (14.17, [M] ⁺), 947 (3.88, [M-Cl] ⁺), 743 (8.31, [M-YCl ₂] ⁺, 575 (18.56, [M-YCl ₂-Cl ₃H ₉] ⁺), 489 (81.06, M/2) ⁺), 453 (100, [M/2-Cl] ⁺) .FT-Raman (cm ^-1): 3067 (m), 1527 (s), 1438 (s), 1338 (vs), 1322 (s), 1209 (s), 1167 (m), 1006 (m), 740 (m), 600 (m), 521 (w), 420 (m), 290 (m).

4. the silica-based bridged fluorenyl cyclopentadiene base of dimethyl Dysprosium trichloride { [Me ₂Si (C ₅H ₄) (C ₁₃H ₈)] [DyCl] ₂(4) preparation

Experimental procedure is with the preparation of title complex 1.With 1.11g (4.13mmol) DyCl ₃Dilithium salt reaction with the part of equimolar amount obtains xanchromatic crystal 0.30g (14.8%), m.p.:240-244 ℃.Ultimate analysis: C ₅₄H ₂₂Si ₂Cl ₂Dy ₂(4): calculated value C, 53.08; H, 4.816. measured value: C, 54.50; H, and 4.27%.MS (EI) (70eV, 50-400 ℃): m/z970 (1.00, [M] ⁺), 4.85 (2.35, [M/2] ⁺), 4450 (2.21, [M/2-Cl] ⁺).

Embodiment 2

1. the silica-based bridged fluorenyl cyclopentadiene base of phenylbenzene Yttrium trichloride { [Ph ₂Si (t-BuC ₅H ₃) (C ₁₃H ₈)] [YCl] ₂(5) preparation

The silica-based bridged fluorenyl tertiary butyl of 4.36g (9.36mmol) phenylbenzene substituted cyclopentadienyl part is dissolved in the ether of 150ml, under the frozen water cooling, slowly drip the hexane solution of the n-Butyl Lithium of 11.7ml (1.6M), solution becomes orange by yellow, room temperature reaction 5 hours.Then the diethyl ether solution of resulting part dilithium salt slowly is added drop-wise to and is cooled to-78 ℃ and is suspended with 1.10g (5.64mmol) YCl ₃The 10ml diethyl ether solution in, slowly be warming up to stirring at room reaction two days.The centrifugation precipitation shifts clear liquid.Vacuum is drained solvent, and the gained solid product shifts extracting solution with the methylbenzene extraction of 50ml, and the slow concentrated solvent of vacuum places-20 ℃ of coolings to separate out yellow crystals 1.23g (37.1%), m.p:315-316 ℃ to 20ml.Ultimate analysis: C ₇₄H ₆₆Si ₂Cl ₂Y ₂(5) calculated value, C, 70.70; H, 5.34. measured value: C, 70.34; H, and 5.57%.MS (EI) (70eV, 50-400 ℃): m/z554 (0.32, [M/2-Cl] ⁺), 302 (100, [C ₁₃H ₈-CPh ₂] ⁺). ¹H NMR (300MHz, C ₆H ₆-D ₆): δ=7.2-8.2 (m, CH (Ar)), 5.6-6.3 (m, CHCp), 1.37 (s, CH ( ^tBu)) .FT-Raman (cm ^-1): 3046 (m), 1587 (s), 1529 (s), 1335 (vs), 1210 (s), 998 (vs), 672 (m), 523 (w), 425 (m), 252 (m).

2. the silica-based bridged fluorenyl tertiary butyl of phenylbenzene substituted cyclopentadienyl Dysprosium trichloride { Ph ₂Si (t-BuC ₅H ₃) (C ₁₃H ₈) [DyCl] ₂(6) preparation

Experimental procedure is with the preparation of title complex 5.With 1.00g (3.72mmol) DyCl ₃Dilithium salt reaction with the part of equimolar amount obtains xanchromatic crystal 1.76g (71.5%), d.p:170 ℃.Ultimate analysis: C ₃₄H ₃₀SiCl ₂Dy (6): calculated value C, 59.56; H, 4.38. measured value: C, 59.66; H, and 4.51%.MS (EI) (70eV, 50-400 ℃): m/z1099 (4.23, [M] ⁺), 665 (60.89, [M/2] ⁺), 630 (17.59, [M/2-Cl] ⁺), 614 (74.16, [M/2-Cl-Me] ⁺), 302 (100, [C ₁₃H ₈-CPh ₂] ⁺).

Embodiment 3

1. phenylbenzene methylene-bridged fluorenyl cyclopentadiene base lutecium chloride (C ₁₃H ₈) CPh ₂(C ₅H ₄) Lu (μ ₂-Cl) ₂Li (THF) ₄(7) preparation

Under the protection of argon gas, with 42ml (0.1M) part dilithium salt (C ₁₃H ₈) CPh ₂(C ₅H ₄) Li ₂Tetrahydrofuran solution be added drop-wise at leisure and be cooled to-78 ℃ be suspended with 1.58g (5.6mmol) LuCl ₃The 20ml tetrahydrofuran solution in, reaction solution slowly rose to room temperature reaction two days.Centrifugation precipitation, clear liquid shifts, and vacuum concentration drips hexane solution at leisure to 10ml in reaction solution, separate out xanchromatic crystal 1.35g (62.8%), m.p after being statically placed in-20 ℃ of following a couple of days:＞320 ℃.Ultimate analysis: C ₃₁H ₂₂LuCl ₂Li: calculated value C, 57.50; H, 3.40; Measured value: C, 57.40; H, 5.43%. ¹H NMR (300MHz; THF-d ₆, 25 ℃): δ=8.04 (d, 2H, J=9.2Hz), 8.01 (d, 2H, J=8.2Hz), 7.90 (d, 2H, J=7.6Hz), 7.10 (t, 2H, J=8.6Hz), 7.09 (m, 4H), 6.97 (t, 2H, J=7.1Hz), 6.84 (t, 2H, J=8.6Hz), 6.48 (d, 2H, J=8.7Hz), 5.92 (t, 2H, J=2.6Hz), 5.82 (t, 2H, J=2.6Hz), FT-Raman (cm ^-1): 3061 (m), 2986 (m), 2889 (m), 1595 (w), 1529 (m), 1436 (m), 1343 (s), 1327 (vs), 1002 (s), 667 (w), 438 (m), 286 (m).

2. phenylbenzene methylene-bridged fluorenyl cyclopentadiene base Yttrium trichloride (C ₁₃H ₈) CPh ₂(C ₅H ₄) Y (μ ₂-Cl) ₂Li (THF) ₄(8) preparation

Experimental procedure is with the preparation method of title complex 7.With 1.40g (7.2mmol) YCl ₃With the reaction of equimolar amount part dilithium salt, obtain xanchromatic crystal 0.94g (41%).Ultimate analysis: C ₄₇H ₅₄YCl ₂LiO ₄: calculated value C, 66.38; H, 6.36; Measured value: C, 65.52; H, 6.33%. ¹H NMR (300MHz; THF-d ₆, 25 ℃): δ=8.08 (d, 2H, J=7.9Hz), 8.00 (d, 2H, J=8.2Hz), 7.90 (d, 2H, J=7.5Hz), 7.29 (t, 2H, J=7.8Hz), 7.09 (m, 4H), 6.98 (t, 2H, J=7.1Hz), 6.81 (t, 2H, J=7.8Hz), 6.52 (d, 2H, J=8.7Hz), 5.90 (t, 2H, J=2.6Hz), 5.81 (t, 2H, J=2.6Hz) .FT-Raman (cm ^-1): 3055 (m), 2888 (m), 2875 (m), 1530 (w), 1435 (m), 1326 (vs), 1003 (s), 668 (w), 438 (w), 286 (m).

Embodiment 4

1. phenylbenzene methylene-bridged fluorenyl cyclopentadiene base hydroboration lanthanum (C ₁₃H ₈) CPh ₂(C ₅H ₄) LaLi (THF) ₄(9) preparation

Under the protection of argon gas, with 37ml (0.05M) part dilithium salt (C ₁₃H ₈) CPh ₂(C ₅H ₄) Li ₂Tetrahydrofuran solution join at leisure and be cooled to-78 ℃ be suspended with 0.85g (1.85mmol) La (BH ₄) ₃(thf) ₃The 15ml tetrahydrofuran solution in reaction solution slowly rose to room temperature reaction 4 hours.The centrifugation precipitation, clear liquid shifts, and vacuum concentration drips hexane solution at leisure to 10ml in reaction solution, and standing over night is separated out bisque crystal 0.35g (22.3%), m.p:144-145 ℃.Ultimate analysis: C ₄₇H ₆₂B ₂LaO ₄Li: calculated value C, 65.70; H, 7.22%; Measured value: C, 64.77; H, and 7.09%.MS (EI) (70eV, 50-400 ℃): m/z764 (9.10, [M-LiBH ₄-THF] ⁺), 165 (100, [C ₁₃H ₉] ⁺). ¹H NMR (300MHz; THF-d ₆, 25 ℃): δ=8.44 (m, 2H), 8.30 (d, 2H, J=7.8Hz), 7.95 (d, 2H, J=8.0Hz), 7.32-7.15 (m, 2H), 7.30 (m, 2H), 7.10 (t, 2H, J=7.2Hz), 6.98 (t, 2H, J=7.2Hz), 6.74 (t, 2H, J=2.6Hz), 6.31 (t, 2H, J=2.6Hz) ,-0.7-0.7 (b, 8H) .FT-Raman (cm ^-1): 3064 (m), 3052 (m), 2984 (m), 2887 (m), 2413 (m), 2218 (m), 1585 (w), 1530 (w), 1436 (m), 1346 (m), 1326 (vs), 1004 (s), 667 (w), 437 (m), 289 (m).

2. phenylbenzene methylene-bridged fluorenyl cyclopentadiene base hydroboration neodymium (C ₁₃H ₈) CPh ₂(C ₅H ₄) Nd (THF) ₄(10) preparation

Experimental procedure is with the preparation method of title complex 9.With 0.89g (1.92mmol) Nd (BH ₄) ₃(FHF) ₃With the reaction of equimolar amount part dilithium salt, obtain yellowish green crystal 0.79g (47.6%), m.p:135-137 ℃.Ultimate analysis: C ₄₇H ₆₂B ₂NdO ₄Li: calculated value C, 65.29; H, 7.18; Measured value: C, 63.77; H, and 6.88%.MS (EI) (70eV, 50-400 ℃): m/z770 (12.03, [M-LiBH ₄-THF] ⁺), 165 (100, [C ₁₃H ₉] ⁺) .FT-Raman (cm ^-1): 3064 (m), 3052 (m), 2984 (m), 2887 (m), 2421 (m), 2221 (m), 1586 (w), 1530 (w), 1436 (m), 1347 (m), 1328 (vs), 1004 (s), 688 (w), 437 (m), 280 (m).

Embodiment 5

1. phenylbenzene methylene-bridged fluorenyl cyclopentadiene base hydroboration neodymium [k (18-crown-6) { (C ₁₃H ₈) CPh ₂(C ₅H ₄) Nd (BH ₄) ₂] ₂[C ₄H ₈O ₂] preparation of (11)

Under the protection of argon gas, with 37.0ml (0.05M) part dilithium salt (C ₁₃H ₈) CPh ₂(C ₅H ₄) K ₂, contain 1-10mmol2, the 1-100mmol tetrahydrofuran solution of 4-dioxane joins at leisure and is cooled to be suspended with 0.85g (1.85mmol) Nd (BH under-78 ℃ ₄) ₃(thf) ₃The tetrahydrofuran solution of 15ml in and to the 18-crown-6 that wherein adds 1ml, reaction solution slowly rose to room temperature reaction 4 hours.The centrifugation precipitation, clear liquid shifts, and vacuum concentration drips hexane solution at leisure to 10ml in reaction solution, and standing over night is separated out bisque crystal 0.35g (20.7%), 202-204 ℃.Ultimate analysis: C ₄₅H ₅₈NdB ₂KO ₇: calculated value C, 59.24; H, 6.19; Measured value C, 59.39; H, and 6.56%.MS (EI) (70eV, 50-400 ℃): m/z770 (12.03, [M-KBH ₄-THF] ⁺), 165 (100, [C ₁₃H ₉] ⁺).

Embodiment 6

1. phenylbenzene methylene-bridged fluorenyl cyclopentadiene base divalence samarium [Ph ₂C (C ₅H ₄) (C ₁₃H ₈)] Sm (THF) _n(12) preparation

Under-78 ℃, 1.57g (3.88mmol) samarium diodide is joined di-potassium 106ml (the 3.9mmol) [Ph of part ₂C (C ₅H ₄) (C ₁₃H ₈)] K ₂Tetrahydrofuran solution in, slowly rose to room temperature reaction two days.Centrifugation precipitation, clear liquid shift and slowly are concentrated into 20ml, and placing a couple of days has a large amount of precipitations to produce.The throw out vacuum is drained, got brown powder 1.06g (45.3%).Ultimate analysis: (n=1): calculated value C, 68.07; H, 4.86. measured value: C, 67.45; H, 4.71%.

Embodiment 7

1. the silica-based bridged fluorenyl cyclopentadiene base of dimethyl alkyl dysprosium [Me ₂Si (C ₅H ₄) (C ₁₃H ₈)] DyCH[TMS] ₂(14) preparation (one-pot synthesis)

Under argon shield, with the dilithium salt [Me of 150ml part ₂Si (C ₅H ₄) (C ₁₃H ₈)] Li ₂(0.038M, diethyl ether solution 5.30mmol) are added drop-wise to and are cooled to-78 ℃ the DyCl that is suspended with at leisure ₃(1.42g in 5.30mmol) the 20ml tetrahydrofuran (THF) or benzene, rose to room temperature reaction two days with reaction solution then at leisure.Under vacuum, reaction solution is extracted, and the toluene solvant of adding 100ml makes it into suspension.Then toluene solution is cooled to-78 ℃, adds 1.03g (6.2mmol) LiCH (TMS) ₂, room temperature reaction one day, reheat to 60 ℃ reaction one day, the solution colour considerable change is an orange, reaction is carried out.Centrifugation precipitation shifts clear liquid, and with the methylbenzene extraction throw out of 50ml, merging clear liquid.Be concentrated into 20ml under the vacuum at leisure, be positioned under-20 ℃ and spend the night, separate out red crystals 0.52g (12.6%), m.p:244-245 ℃.Ultimate analysis: C ₂₇H ₃₇Si ₃Dy (14), calculated value C, 51.25; H, 5.91. measured value: C, 47.90; H, and 6.55%.MS (EI) (70eV, 50-400 ℃): m/z609 (1.29, [M] ⁺), 594 (7.51, M-Me) ⁺), 450 (100, [M-CH (TMS) ₂] ⁺), 145 (30.38, [CH (TMS) ₂] ⁺) .FT-Raman (cm ^-1): 3047 (s), 2899 (vs), 1531 (m), 1322 (s), 1210 (m), 742 (m), 657 (m), 577 (m), 520 (w), 431 (m), 378 (m), 236 (s).

2. the silica-based bridged fluorenyl cyclopentadiene base of dimethyl alkyl erbium [Me ₂Si (C ₅H ₄) (C ₁₃H ₈)] ErCH[TMS] ₂(15) preparation (one-pot synthesis)

Experimental procedure is with the preparation method of title complex 14.With 1.47g (5.35mmol) ErCl ₃After equimolar amount part dilithium salt reaction, again in toluene with 1.03g (6.2mmol) LiCH (TMS), reaction obtains the crystal 0.24mg (7.3%) of orange.Ultimate analysis: C ₂₇H ₃₇Si ₃Er (15): calculated value C, 52.85; H, the real side value of 6.04.: C, 51.00; H, and 6.21%.MS (EI) (70eV, 50-400 ℃): m/z613 (2.13, [M] ⁺), 598 (2.08, [M-Me] ⁺), 454 (100, [M-CH (TMS) ₂] ⁺), 145 (46.84, [CH (TMS) ₂] ⁺) .FT-Raman (cm ^-1): 3048 (m), 2896 (m), 1530 (s), 1324 (vs), 1211 (s), 742 (m), 657 (m), 578 (m), 520 (w), 431 (m), 378 (m), 239 (s).

Embodiment 8

1. the silica-based bridged fluorenyl cyclopentadiene base of dimethyl amido dysprosium [Me ₂Si (C ₅H ₄) (C ₁₃H ₈)] DyN[TMS] ₂(16) preparation (one-pot synthesis)

Under argon shield, with the dilithium salt [Me of 150ml part ₂Si (C ₅H ₄) (C ₁₃H ₈)] Li ₂(0.038M, diethyl ether solution 5.69mmol) are added drop-wise to and are cooled to-78 ℃ the DyCl that is suspended with at leisure ₃(1.53g in 20ml tetrahydrofuran (THF) 5.69mmol), rose to room temperature reaction two days with reaction solution then at leisure.Under vacuum, reaction solution is extracted, and the toluene solvant of adding 100ml makes it into suspension.Then toluene solution is cooled to-78 ℃, adds 1.05g (5.3mmol) KN (TMS) ₂, room temperature reaction one day, reheat to 60 ℃ reaction one day, the solution colour considerable change is red, reaction is carried out.Centrifugation precipitation shifts clear liquid, and with the methylbenzene extraction throw out of 50ml, merging clear liquid.Be concentrated into 20ml under the vacuum at leisure, be positioned under-20 ℃ and spend the night, separate out red crystals 1.32g (39.3%), m.p:114-120 ℃.Ultimate analysis: C ₂₆H ₃₆Si ₃NDy (16), calculated value C, 51.20; H, 5.91; N, 2.30. measured value: C, 50.71; H, 6.05; N, and 2.67%.MS (EI) (70eV, 50-400 ℃): m/z610 (100, [M] ⁺), 594 (47.90, [M-Me] ⁺), 450 (75.55,, [M-N (TMS) ₂] ⁺), 146 (47.41, [N (TMS) ₂] ⁺) .FT-Raman (cm ^-1): 3047 (s), 2898 (vs), 1526 (m), 1322 (m), 1009 (m), 742 (w), 655 (w), 610 (w), 430 (w), 377 (m), 237 (s).

2. the silica-based bridged fluorenyl cyclopentadiene base of dimethyl amido erbium [Me ₂Si (C ₅H ₄) (C ₁₃H ₈)] ErN[TMS] ₂(17) preparation (one-pot synthesis)

Experimental procedure is with the preparation method of title complex 16.With 1.30g (4.76mmol) ErCl ₃After equimolar amount part dilithium salt reaction, again in toluene with 1.08g (5.4mmol) KN (TMS) ₂, reaction obtains xanchromatic crystal 0.33g (11.5%).M.p：226-228℃。Ultimate analysis: C ₂₆H ₃₆Si ₃Er (16): calculated value C, 50.81; H, 5.86; N, the real side value of 2.28.: C, 50.68; H, 6.03; N, and 2.51%.MS (EI) (70eV, 50-400 ℃): m/z 615 (18.30, [M] ⁺), 599 (9.31, [M-Me] ⁺), 453 (6.98, [M-N (TMS) ₂] ⁺), 146 (100, [N (TMS) ₂] ⁺) .FT-Raman (cm ^-1): 3040 (m), 2899 (m), 1527 (s), 1324 (vs), 1211 (s), 743 (m), 656 (m), 614 (m), 520 (w), 410 (m), 378 (m), 240 (s).

3. phenylbenzene methylene-bridged fluorenyl cyclopentadiene base amido lutetium [Ph ₂C (C ₅H ₄) (C ₁₃H ₈) LuN (TMS) ₂(18) preparation

With 0.77g (1.27mmol) (C ₁₃H ₈) CPh ₂(C ₅H ₄) Lu (μ ₂-Cl) ₂Li (THF) ₄Be suspended in the toluene of 50ml, be cooled to-78 ℃ and add 0.23g (1.15mmol) KN (TMS) down ₂, rose to room temperature reaction two days.The centrifugation precipitation, clear liquid shifts, and is concentrated into 30ml, is positioned under-20 ℃, separates out the crystal 0.09g (12.6%) of orange, m.p:170 ℃.Ultimate analysis: C ₃₇H ₄₀Si ₂NLu (18): calculated value C, 60.91; H, 5.49; N, 1.92. measured value: C, 62.64; H, 5.63; N, and 2.09%.MS (EI) (70eV, 50-400 ℃): m/z730 (19.14, [M] ⁺), 654 (21.91, [M-Ph] ⁺), 146 (65.71, [N (TMS) ₂] ⁺) .1H NMR (300 MHz; C ₆H ₆-D ₆, 25 ℃): δ=8.25 (d, 2H, J=8.2Hz, CH (Ar)), 8.14 (d, 2H, J=6.5Hz, CH (Ar)), 8.0 (d, 2H, J8.1Hz, CH (Ar)), 7.0-7.5 (m, CH (Ar)), 6.11 (m, 2H, CH (Cp)), 6.30 (m, 2H, CH (Cp)), 0.35 (s, 3H, CH ₃(Si)) ,-0.20 (s, 15H, CH ₃(Si)) .FT-Raman (cm ^-1) ∷ 3056 (m), 2898 (m), 1528 (m), 1435 (m), 1327 (vs), 1003 (s), 741 (m), 667 (m), 618 (m), 522 (w), 440 (m), 285 (m).

Experimental example 8

Adopt previous reaction condition and different substituting group substrate synthetic dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compoundings, the results are shown in Table 13 for it.

Table 13

Title complex R1 2 R3 R4 R5 R6 R7 X1 X2 M productive rate %

19 H H H H H H C Ph N(TMS) ₂ Lu 12.6

20 H CH ₃?CH ₃ H t-Bu t-Bu Ge Et CH ₃ Sm 27.4

21 CH ₃ H ₃ CH ₃ CH ₃?Si(CH ₃) ₃?Si(CH ₃) ₃Sn CH ₃ i-Pr Sc 35.3

22 H H H H H H Si CH ₃ CH ₂(TMS) Lu 15.5

23 H H H H H H Si CH ₃ H Yb 14.6

24 H H H H t-Bu t-Bu Si H CH ₂(TMS) Lu 20.7

Embodiment 9

Title complex 19:

Ultimate analysis: calculated value C, 60.91; H, 5.49; N, 1.92. measured value: C, 62.64; H, 5.63; N, and 2.09%.MS (EI) (70eV, 50-400 ℃): m/z 730 (19.14, [M] ⁺), 654 (21.91, [M-Ph] ⁺), 146 (65.71, [N (TMS) 2] ⁺). ¹H NMR (300MHz; C ₆H ₆D ₆25 ℃): δ=8.25 (d, 2H, J=8.2Hz, CH (Ar)), 8.14 (d, 2H, J=6.5Hz, CH (Ar)), (8.0 d, 2H, J=8.1Hz, CH (Ar)), 7.0-7.5 (m, CH (Ar)), 6.11 (m, 2H, CH (Cp)), 6.30 (m, 2H, CH (Cp)), 0.35 (s, 3H, CH ₃(Si)) ,-0.20 (s, 15H, CH ₃(Si)).

Title complex 20:

Ultimate analysis: calculated value C, 50.00; H, 5.69. measured value: C, 50.68; H, and 5.63%.MS (EI) (70eV, 50-400 ℃): m/z792 (16.14, [M] ⁺), 777 (24.61, [M-Me] ⁺).

Title complex 21:

Ultimate analysis: calculated value C, 62.20; H, 7.70. measured value: C, 62.68; H, and 7.93%.MS (EI) (70eV, 50-400 ℃): m/z636 (25.75, [M] ⁺), 593 (47.58, [M-iPr] ⁺).

Title complex 22:

Ultimate analysis: calculated value C, 56.39; H, 5.45. measured value: C, 57.32; H, 6.04%. ¹H NMR (300MHz; C ₆H ₆-D ₆25 ℃): δ 8.00 (d, 2H, Flu, J=8.3Hz), 7.82 (d, 2H, Flu, J=8.6Hz), 7.30 (m, 2H, Flu), 7.22 (m, 2H, Flu), 6.24 (t, 2H, Cp, J=2.6Hz), 5.85 (t, 2H, Cp, J=2.6Hz), 0.38 (s, 6H, SiMe ₂) .-0.02 (s, 9H, SiMe ₃) .MS (EI) (70eV, 50-400 ℃): m/z532 (5.23, [M] ⁺), 345 (69.34, [M-CH ₂(TMS)] ⁺).

Title complex 23:

Ultimate analysis: calculated value C, 53.40; H, 4.03. measured value: C, 54.08; H, and 4.73%.MS (EI) (70eV, 50-400 ℃): m/z472 (0.48, [M] ⁺), 307 (27.69, [M-Flu] ⁺).

Title complex 24:

Ultimate analysis: calculated value C, 57.78; H, 6.44. measured value: C, 57.64; H, 6.25%. ¹H NMR (300MHz; C ₆H ₆-D ₆): δ 8.12 (d, 2H, Flu, J=8.3Hz), 7.87 (d, 2H, Flu, J=8.6Hz), 7.40 (m, 2H, Flu), 6.46 (t, 2H, Cp, J=2.6Hz), 5.90 (t, 2H, Cp, J=2.6Hz), 1.82 (s, 1 8H, t-Bu) .-0.02 (s, 9H, SiMe ₂) .MS (EI) (70eV, 50-400 ℃): m/z 644 (2.36, [M] ⁺), 571 (100, [M-CH ₂(TMS)] ⁺).

Claims

1. dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding { [(X with following molecular formula ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶)] MX ²(L) _n} _m,

Have following structural formula:

R wherein ¹, R ³Or R ⁴=H or CH ₃, R ²=H, R ⁵Or R ⁶=H, C _1-4Alkyl or Si (CH ₃) ₃, R ⁷=Si, C, Ge or Sn, X ¹=C _1-4Alkyl or phenyl, X ²=Cl, BH ₄, H, C _1-4Alkyl, N[(CH ₃) ₃Si] ₂, CH[(CH ₃) ₃Si] ₂, CH ₂[(CH ₃) ₃Si] or THF, M=lanthanon, yttrium or scandium, L=(CH ₃) ₃Si, Li (THF) ₄, [Y-crown ether] or [Y-crown ether]-2,4 epoxies six ring, n=1 or 0, m=1 or 2, when m=2, n=0, Y=monovalence metal, crown ether=hexaoxacyclooctadecane-6-6 or 15-crown ether-5, THF=tetrahydrofuran (THF).

Perhaps: R ¹, R ², R ³, R ⁴, R ⁵, R ⁶Be H, R ⁷Be C, X ¹Be phenyl, X ²Be Cl, M=lanthanon, yttrium or scandium, L=ClLi (THF) ₄, n=1, m=1;

Perhaps: R ¹, R ², R ³, R ⁴, R ⁵, R ⁶Be H, R ⁷Be C, X ¹Be phenyl, X ²Be BH ₄, M=lanthanon, yttrium or scandium, L=BH ₄Li (THF) ₄, n=1, m=1;

Perhaps: R ¹, R ², R ³, R ⁴, R ⁵, R ⁶Be H, R ⁷Be C, X ¹Be phenyl, X ²Be THF _n, M=lanthanon, yttrium or scandium, n=0, m=1;

2. one kind has dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding as claimed in claim 1, it is characterized in that having following structural formula:

Or

Wherein M according to claim 1, Ph=phenyl, the t-Bu=tertiary butyl.

3. one kind has dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding as claimed in claim 1, it is characterized in that having following structural formula:

Wherein M according to claim 1, E=CH or N.

4. one kind has dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding as claimed in claim 1, it is characterized in that having following structural formula:

Ph phenylbenzene wherein, M according to claim 1.

5. one kind has dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding as claimed in claim 1, it is characterized in that having following structural formula:

Wherein M and THF are according to claim 1.

6. one kind has dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding as claimed in claim 1, it is characterized in that having following structural formula:

M and L are according to claim 1 in the base.

7. one kind has dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding as claimed in claim 1, it is characterized in that having following structural formula:

Wherein M and N are according to claim 1.

8. synthetic method with dialkyl methylene-bridged fluorenyl cyclopentadiene base rare earth compounding as claimed in claim 1, it is synthetic to it is characterized in that having following method:

(1) molecular formula is (X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶) Y ₂Univalent metal salt and equimolar MCl ₃Or M (BH ₄) ₃(THF) ₃To room temperature, react 1-50h for-78 ℃ in the tetrahydrofuran solvent neutralization, generate { [(X ¹) ₂(R ²) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶)] [MCl] _n, (X ¹) ₂(R ²) (C ₅R ¹R ²R ³R ⁴) M (μ ₂-Cl) ₂Li-(THF) ₄Or (X ¹) ₂(R ²) (C ₅R ¹R ²R ³R ⁴) M (BH ₄) ₂Li (THF) ₄

(2) molecular formula is (X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶) Y ₂, M (BH ₄) ₃(THF) ₃And the mol ratio of hexaoxacyclooctadecane-6-6 or 15-crown ether-5 is 1: 1: during 1-100, react 1-5h generation [Y (hexaoxacyclooctadecane-6-6 or 15-crown ether-5)] { (X with-78 ℃ at organic solvent to room temperature ¹) ₂R ⁷(C ₅R ¹R ²R ³R ⁴) M (C ₁₃H ₆R ⁵R ⁶) M (BH ₄) ₂;

(3) molecular formula is (X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶) Y ₂, M (BH ₄) ₃(THF) ₃, hexaoxacyclooctadecane-6-6 or 15-crown ether-5 and 2, the mol ratio of 4-dioxane is 1: 1: 1-100: 1: 100 o'clock, reaction 1-5h to the room temperature generated [Y (hexaoxacyclooctadecane-6-6 or 15-crown ether-5)] { (X organic solvent and-78 ℃ ¹) ₂R ⁷(C ₅R ¹R ²R ³R ⁴) M (C ₁₃H ₆R ⁵R ⁶) M (BH ₄) ₂} ₂[C ₄H ₈O ₂];

(4) molecular formula is (X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶) Y ₂To room temperature, react 10-50h at-78 ℃ with equimolar samarium diodide or ytterbium, generate (X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶)-Sm or Yb-(THF) _m

(5) molecular formula is (X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶) Y ₂MCl in organic solvent ₃With equimolar YCH (TMS) ₂Or YN (TMS) ₂,, generate [(X at-78 ℃ to 60 ℃ reaction 10-80h ¹) ₂(R ⁷)-(C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶)] MCH (TMS) ₂Or [(X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶)] MN-(TMS) ₂

(6) with (X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶) M (μ ₂-Cl) ₂Y (THF) ₄YN-(TMS) with mole ₂To room temperature, react 20-50h for-78 ℃ in the organic solvent neutralization, generate [(X ¹) ₂(R ⁷) (C ₅R ¹R ²R ³R ⁴) (C ₁₃H ₆R ⁵R ⁶)] NM (TMS) ₂

9. the synthetic method with dialkyl methylene bridge difluorenyl cyclopentadienyl alkene soil title complex as claimed in claim 8 is characterized in that adopting the solvent recrystallization method to obtain monocrystalline.

10. purposes with dialkyl methylene bridge difluorenyl cyclopentadienyl alkene as claimed in claim 1 soil title complex is characterized in that being used for the catalyzer of polyreaction.