CN101031595A - Single component cationic palladium proinitiators for the latent polymerization of cycloolefins - Google Patents

Abstract

Palladium compound compositions are provided in accordance with Formulae [((R)3E)aPd(Q)(LB)b]p[WCA]r, where ((R)3E) is a Group 15 electron donor ligand, Q is an anionic ligand, LB is a Lewis base, WCA is a weakly coordinating anion, a is 1, 2 or 3, b is 0, 1 or 2, the sum of a and b is 1, 2 or 3 and each of p and r is an integer such that the molecular charge is zero, or [(E(R)3)(E(R)2*)Pd(LB)]p[WCA]r where E(R)2R* represents a Group 15 neutral electron donor ligand and where R* is an anionic hydrocarbyl containing moiety, bonded to the Pd and having a ss hydrogen with respect to the Pd center. Such compound composition exhibits latent polymerization activity in the presence of polycyclic olefins.

Description

One-component cationic palladium pre-initiator for the latent polymerization of cycloolefins

Cross reference to related U.S. applications

The present application claims priority from U.S. provisional application serial No. 60/516054 entitled "one-component cationic palladium pro-initiator for the latent polymerization of cycloolefins" filed on 31/10/2003.

Technical Field

The present invention relates generally to palladium compound compositions suitable for use in forming polymerization initiators and stable intermediates thereof, and more particularly to cationic palladium pro-initiator compositions useful in forming latent palladium catalyst compositions for polymerization of polycycloolefin monomers.

Background

The prior art contains many disclosures of catalysts for the polymerization of cyclic olefin monomers. These disclosures include catalysts comprising a group 10 metal cation and a weakly coordinating anion. However, these catalysts of the prior art have certain limitations in their use. For example, it must be prepared in situ so that the polymerization of the monomer is immediately initiated.

U.S. Pat. No. 6,455,650 entitled "catalyst and Process for the polymerization of cycloalkenes" is one of such prior art references disclosing catalysts having a group 10 metal cation and a weakly coordinating anion. The group 10 metal cation of this patent contains anionic hydrocarbyl ligands which are important in forming the active catalyst sites. This patent discloses various methods for preparing a catalyst having a group 10 metal complex containing an anionic hydrocarbyl ligand in the presence of a cyclic olefin monomer such that the resulting catalyst mixture immediately initiates polymerization of the monomer. The catalyst prepared by the process of this patent cannot be isolated. Furthermore, the patent does not suggest that the catalyst disclosed therein can be isolated and used later for the polymerization of cycloolefin monomers.

JP 1996-325329A also discloses catalysts obtained by mixing a group 10 transition metal compound with an optional triarylphosphine ligand and a cocatalyst. Typical cocatalysts include aluminum alkyls, Lewis acids or compounds that form ionic complexes including Weakly Coordinating Anion (WCA) salts. Specifically, the publication discloses that a reaction liquid consisting of (a) a liquid monomer to be polymerized, (b) a group 10 transition metal compound and (c) a cocatalyst is injected into a mold to form an in-mold polymer. Thus, as with the U.S. Pat. No. 6,455,650 patent, this publication also teaches the formation of an active catalyst (in situ) in the presence of cyclic olefin monomer and the immediate initiation of the polymerization of the monomer. Also as in US6,455,650, this publication does not suggest that the catalyst can be separated out.

In addition to the solution polymerization disclosedin U.S. Pat. No. 6,455,650 and JP 1996-325329A, the polymerization of cycloolefins can also be carried out in the absence or in the absence of solvents. This polymerization is commonly referred to as bulk polymerization and is suitable for forming applications such as chip encapsulants. Bulk polymerization systems generally comprise two parts kept separate from each other, each of which has a catalyst precursor and one or more monomers. To be polymerized, the two separate fractions are mixed to form the active catalyst species and the monomers present immediately begin to polymerize. Unlike solution polymerization, bulk polymerization systems require stringent formulation parameters to ensure that there is an appropriate stoichiometric amount of catalyst component suitable for efficient polymerization and the polymer product has the desired physical property profile due to the inability to remove excess catalyst and/or catalyst precursor. Furthermore, since the mixture is usually dispensed in multiple portions once the two-part system is mixed, the "life" of the mixture for such dispensing can be problematic because the monomers begin to polymerize as soon as the catalyst components are combined together, thereby becoming too viscous to dispense.

Thus, for bulk polymerization, it is advantageous to have a portion of the latent system (i.e., a one-component pro-initiator in monomer that can be triggered to begin substantial polymerization). A significant advantage of such systems over currently known two-part systems is that they are easier to use because there is no need to mix the parts and they can be dispensed for long periods of time without significant changes in viscosity. In addition, such a single part system does not have the difficulties associated with formulations in two separate parts, errors in mixing those parts before use, and the potential for excessive waste due to expiration of the mixture before the amount of mixing is consumed. It is clear that the use of isolatable latent pro-initiators in solvent polymerization systems may also be advantageous. For example, this separable pre-initiator can be mass-produced to reduce production costs, and its activity can be measured before it is used to initiate polymerization to reduce the cost of the desired polymer by not requiring an excess of initiator to ensure the desired conversion. Furthermore, the one-component pro-initiators enable better control of the metering polymerization. Thus, there is a need for such a one-component latent pro-initiator system to provide at least the above-mentioned advantages.

Drawings

Specific embodiments of the present invention are described below with reference to the following drawings.

FIG. 1 is a schematic representation of proposed mechanisms and reactions for forming various triisopropylphosphine derivatives (A, B, C, D, E, F, G, H and I) of the present invention; and

fig. 2, 3 and 4 are structural illustrations of palladium complexes according to embodiments of the invention.

Detailed Description

Exemplary embodiments of the present invention are described below. These embodiments relate to latent one-component cationic palladium pro-initiators for the solution and/or bulk polymerization of cyclic olefins. Various modifications, adaptations, or variations of the exemplary embodiments described herein will be apparent to those skilled in the art. It should be understood that all such modifications, adaptations or variations that rely upon the teachings of the present invention and through which these teachings have advanced the art are considered to be within the scope and spirit of the present invention.

Embodiments of the present invention include latent mono-component palladium compositions having a coordinated palladium metal cation and a weakly coordinated anion. Advantageously, such coordinated palladium metal cations and weakly coordinating anions have been found to be suitable as potential polymerization initiators for cyclic olefin monomer compositions. In certain embodiments, the complexed palladium metal cation and weakly coordinating anion are suitable for use in forming latent polymerization initiators, such as metallated ligands and hydrogenated palladium cations and weakly coordinating anions. Other exemplary embodiments according to the present invention include the preparation of hydrogenated palladium and deuterides by pyrolysis of this coordinated palladium metal cation and weakly coordinated anion and appropriately alternating reaction sequences, as described below. Some exemplary embodiments of the invention include palladium cations having a group 15 neutral electron donor ligand, an anionic ligand, and a weakly coordinating anion. Other exemplary embodiments include palladium metal cations having a group 15 neutral electron donor ligand, an anionic ligand, a lewis base ligand, and a weakly coordinating anion. Other exemplary embodiments include palladium metal cations having anionic ligands, chelate-coordinated phosphine ligands, Lewis base ligands, and weakly coordinating anions.

Advantageously, the active initiator of the pro-initiator according to the invention is not derived from neutral hydrocarbon groups, nor from the protonation of any organometallic additives or metal centers. Without wishing to be bound by any theory, it is believed that the active initiator species of such pro-initiators are formed by abstraction of intramolecular hydride or deuterium anion from the base group 15 ligand to produce the desired cationic palladium hydride. Thus, the pro-initiators of the present invention are particularly advantageous because they do not have to be formed in situ. Instead, they can be added to the monomer polymerization medium prior to polymerization to begin abstracting intramolecular hydride ions when desired.

Thus, the pro-initiators of the present invention are latent, i.e., they are substantially non-reactive in the presence of cyclic olefin monomers before being specifically activated. Activation is usually accomplished by subjecting the pro-initiator to an energy source. Typical energy sources include, but are not limited to, heat (to or above a particular temperature), actinic radiation (but also X-ray and electron beam radiation) and acoustic energy. Furthermore, since the palladium hydride initiator (as described later) is the product of the ligand-derived metallation step and subsequent elimination sequence, it is possible to take advantage of the kinetic isotope effect of deuterium to further extend the incubation period of the initiator and even further reduce the reaction rate. In addition, potential intermediates of the pro-initiator can be isolated and used as equivalent species.

Description of the initiator System

The pre-initiator of the present invention contains a palladium metal cation and a weakly coordinating anion as shown in formulas Ia and Ib below:

[(E(R)₃)_aPd(Q)(LB)_b]_p[WCA]_r(Ia)

[(E(R)₃)(E(R)₂R*)Pd(LB)]_p[WCA]_r(Ib)

in the formula Ia, E (R)₃Represents a group 15 neutral electron donor ligand wherein E is selected from the group consisting of group 15 elements of the periodic table of the elements and R independently represents hydrogen (or one of its isotopes), or a moiety containing an anionic hydrocarbyl group; q is an anionic ligand selected from carboxylate, thiocarboxylate, and dithiocarboxylate groups; LB is a Lewis base; WCA represents a weakly coordinating anion; a represents an integer of 1, 2 or 3; b represents an integer of 0, 1 or 2, wherein the sum of a + b is 1, 2 or 3; p and r are integers representing the multiple of the palladium cation and weakly coordinating anion used to structurally balance charge in formula Ia. In a typical embodiment, p and r are independently selected from integers of 1 and 2.

In the formula Ib, E (R)₃As defined for formula I a, E (R)₂R also represents a group 15 neutral electron donor ligand, wherein E, R, R and p are as previously defined, wherein R is an anionic hydrocarbyl containing moiety bonded to Pd and having β hydrogens relative to the center of Pd.In a typical embodiment, p and r are independently selected from integers of 1 and 2.

The Weakly Coordinating Anion (WCA) is defined herein as a generally larger and bulky anion capable of delocalizing its negative charge, which is only weakly coordinated to the palladium cation of the present invention and is sufficiently labile to be displaced by a solvent, monomer, or neutral Lewis base. More specifically, the WCA functions as a stabilizing anion for the palladium cation but does not transfer to the cation to form a neutral product. The WCA is relatively inert, it is not oxidizing, reducing and nucleophilic.

The importance of WCA charge delocalization depends to some extent on the nature of the transition metal-containing cationic active species. It is advantageous that the WCA is not coordinated to the transition metal cation or is only weakly coordinated to this cation. Furthermore, it is also advantageous that the WCA does not transfer anionic substituents or fragments to cations so that the transfer results in the formation of neutral metal compounds and neutral by-products. Thus, WCAs suitable for usein accordance with the present invention are those which are compatible, which are cationic stabilized in the sense of balancing their ionic charge, and which retain sufficient volatility to be displaced by ethylenically unsaturated monomers during polymerization. Further, suitable WCAs are those having a molecular size sufficient to partially inhibit or help prevent neutralization of the late transition metal cation by Lewis bases other than the polymerizable monomer that may be present during polymerization. While not wishing to be bound by any theory, it is believed that WCAs according to embodiments of the present invention may include anions (arranged by at least more than one coordination), such as triflate (CF)₃SO₂ ^-) Tris (trifluoromethyl) methine ((CF)₃SO₂)₃ ^-)、triflimide、BF₄ ^-、BPh₄ ^-、PF₆ ^-、SbF₆ ^-Tetrakis (pentafluorophenyl) borate (abbreviated herein as FABA), and tetrakis [3, 5-bis (trifluoromethyl) phenyl]Borate ([ BAR)^f]^-). Furthermore, it is believed that the catalytic activity of the pro-initiators of the invention increases with decreasing coordination of the WCA and that the formulation latency increases with increasing coordination of the WCA. Thus, it is believed that to achieve a period between catalytic activity and latencyTo be balanced, WCA and ER₃The selection should be made in coordination with each other.

The neutral electron donor is defined herein as any ligand that has a neutral charge in its closed shell electron configuration when removed from the palladium metal center.

The anionic hydrocarbyl moiety is defined herein as any hydrocarbyl group that has a negative charge in its closed shell electron configuration when removed from 'E' (see formula Ia).

The lewis base described herein is defined as "a basic substance that donates a pair of electrons to a chemical bond" and thus it is a donor of electron density.

In an embodiment according to the invention, E is selected from elements of group 15 of the periodic Table of the elements, more particularly from phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi). In formula Ia, the anionic hydrocarbyl containing moieties R are independently selected from the group consisting of, but not limited to, H, linear and branched (C)₁-C₂₀) Alkyl, (C)₃-C₁₂) Cycloalkyl group, (C)₂-C₁₂) Alkenyl, (C)₃-C₁₂) Cycloalkenyl group, (C)₅-C₂₀) Polycyclic alkyl radical, (C)₅-C₂₀) Polycyclic alkenyl group, and (C)₆-C₁₂) Aryl, and two or more R groups together with E may form a heterocyclic or heteropolycyclic ring containing 5 to 24 atoms. In formula Ib, the anionic hydrocarbyl containing moiety R is selected from, but not limited to, linear and branched (C)₂-C₂₀) Alkyl, (C)₃-C₁₂) Cycloalkyl group, (C)₂-C₁₂) An alkenyl group,(C₃-C₁₂) Cycloalkenyl group, (C)₅-C₂₀) Polycyclic alkyl radical, (C)₅-C₂₀) Polycycloalkenyl, provided that the anionic hydrocarbyl containing moiety has at least one β hydrogen relative to the center of the Pd when bonded to the Pd.

Typical alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and neopentyl. Typical alkenyl groups include, but are not limited to, vinyl, allyl, isopropenyl, and isobutenyl. Typical cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Typical polycyclic alkyl groups include, but are not limited to, norbornyl and adamantyl. Typical polycyclic alkenyl groups include, but are not limited to, norbornenyl and adamantyl. Typical aryl and aralkyl groups include, but are not limited to, phenyl, naphthyl, and benzyl.

In certain exemplary embodiments of the invention, the group 15 neutral electron donor ligand is a phosphine ligand. Advantageous exemplary phosphine ligands include di-t-butylcyclohexylphosphine, dicyclohexyl-t-butylphosphine, tricyclohexylphosphine, tricyclopentylphosphine, dicyclohexyladamantylphosphine, cyclohexyldiadamantylphosphine, triisopropylphosphine, di-t-butylisopropylphosphine, and diisopropyl-t-butylphosphine.

Typical phosphine ligands also include tri-n-propylphosphine, tri-t-butylphosphine, di-n-butyladamantylphosphine, dinorbornylphosphine, t-butyldiphenylphosphine, isopropyldiphenylphosphine, dicyclohexylphenylphosphine, di-t-butylisopropylphosphine, diisopropylt-butylphosphine, di-t-butylneopentylphosphine, and dicyclohexylneopentylphosphine.

Other typical phosphine ligands include, but are not limited to, trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-butylphosphine, tri-sec-butylphosphine, triisobutylphosphine, tricyclopropylphosphine, tricyclobutylphosphine, tricycloheptylphosphine, isopropenyldiisopropylphosphine, cyclopentenyldicyclopropenylphosphine, cyclohexenyldicyclohexylphosphine, triphenylphosphine, trinaphthylphosphine, tribenzyldiphenylphosphine, benzyldiphenylphosphine, di-n-butyladamantylphosphine, allyldiphenylphosphine, vinyldiphenylphosphine, cyclohexyldiphenylphosphine, di-t-butylphenyl-phenylphosphine, diethylphenylphosphine, dimethylphenylphosphine; diphenylpropylphosphine, ethyldiphenylphosphine, tri-n-octylphosphine, tribenzylphosphine, 4, 8-dimethyl-2-phosphabicyclo [3.3.1]nonane and 2, 4, 6-triisopropyl-1, 3-dioxa-5-phosphane.

In other exemplary embodiments of the invention, the group 15 neutral electron donor ligand is an arsine ligand. Exemplary arsine ligands that are favored include tricyclohexylarsine, tricyclopentylarsine, di-t-butylcyclohexylarsine, dicyclohexylt-butylarsine, triisopropylarsine, di-t-butylisopropylarsine, and diisopropylt-butylarsine.

Typical arsine ligands also include dicyclohexyladamantylalarsine, cyclohexyldiadamantylarsine, di-n-butyladamantylarsine, dinonylarsine, t-butyldiphenylarsine, isopropyldiphenylethane, dicyclohexylphenylarsine, and dicyclohexylneopentylgarsine.

Other typical arsine ligands include, but are not limited to, trimethylarsine, triethylarsine, tri-n-propylarsine, triisopropylarsine, tri-n-butylaarsine, tri-sec-butylaarsine, triisobutylaarsine, tri-tert-butylaarsine, tricyclopropylalarsine, tricyclobutylalarsine, tricycloheptylarsine, isopropenyldiisopropylarsine, cyclopentenyldicyclopropenylarsine, cyclohexenyldicyclohexylarsine, triphenylarsine, trinaphthylarsine, tribenzylarsine, benzyldiphenylarsine, allyldiphenylarsine, vinyldiphenylarsine, cyclohexyldiphenylarsine, di-tert-butylphenyl arsine, diethylphenylarsine, dimethylphenylarsine, diphenylpropylarsine, ethyldiphenylarsine, tri-n-octylarsine, tribenzylarsine, di-tert-butylisopropylarsine, diisopropyl tert-butylarsine, and di-tert-butylneopentylgarsine.

In other exemplary embodiments of the invention, the group 15 neutral electron donor ligand is a ligand. Advantageous exemplary ligands include tricyclohexyl, di-tert-butylcyclohexyl, cyclohexyl di-tert-butyl, triisopropyl, di-tert-butylisopropyl, and diisopropyl tert-butyl.

Typical ligands also include dicyclohexyladamantyl, cyclohexyldiadamantyl, dicyclohexylt-butyl, dinorbornyl, t-butyldi (t-butylglistenine), isopropyldiphenyl, dicyclohexylphenyl, and dicyclohexylneopentyl.

Other typical ligands include, but are not limited to, trimethyl, triethyl,tri-n-propyl, triisopropyl, tri-n-butyl, tri-sec-butyl, triisobutyl, tri-tert-butyl, tricyclopropyl, tricyclobutyl, tricyclopentyl, tricycloheptyl, isopropenyldiisopropyl, cyclopentenyldicyclopropenyl, cyclohexenyldicyclohexyl, triphenyl, trinaphthyl, tribenzyl, benzyldiphenyl, di-n-butyladamantyl, dinonylnorbornyl, tert-butyldiphenyl, allyldiphenyl, vinyldiphenyl, cyclohexyldiphenyl, di-tert-butylphenyl, diethylphenyl, dimethylphenyl, diphenylpropyl, ethyldiphenyl, tri-n-octyl, tribenzyl, di-tert-butylisopropyl, diisopropyltert-butyl, and di-tert-butylneopentyl.

In yet another exemplary embodiment of the invention, the group 15 neutral electron donor ligand is

A ligand. Advantageous exemplary

The ligand comprising tricyclohexyl

And diisopropyl tert-butyl

Typically, a

The ligands also include dicyclohexyladamantyl

Cyclohexyl diamantanyl radical

Dicyclohexyl tert-butylDi-norbornyl

Tert-butyl di

(t-butylbismuthine), isopropyldiphenyl

Dicyclohexylphenyl

Di-tert-butyl isopropyl

Diisopropyl tert-butyl

And dicyclohexylneopentylgroup

Other typical bismuth ligands include, but are not limited to, trimethylbismuth, triethylbismuth, tri-n-propylbismuth, triisopropylbismuth, tri-n-butylbismuth, tri-sec-butylbismuth, triisobutylbismuth, tri-tert-butylbismuth, di-tert-butylcyclohexylbismuth, dicyclohexyl-tert-butylbismuth, tricyclopropylbuthium, tricyclobutylbuthiumTricyclopentylbismuth, tricyclohexylbismuth, isopropenyldiisopropylbismuth, cyclopentenyldicyclopropenylbismuth, cyclohexenyldicyclohexylbismuth, triphenylbismuth, trinaphthylbis, tribenzylbismuth, benzyldiphenylbismuth, dicyclohexyladamantyl bismuth, cyclohexyldiadamantyl bismuth, di-n-butyladamantyl bismuth, dinonylbismuth, tert-butyldiphenylbismuth, allyldiphenylbismuth, vinyldiphenylbismuth, cyclohexyldiphenylbismuth, di-tert-butylphenyl bismuth, diethylphenyl bismuth, dimethylphenyl bismuthDiphenylpropylbismuth, ethyldiphenylbismuth, tri-n-octylbismuth, isopropyldiphenylbismuth, dicyclohexylphenylbismuth, tribenzylbismuth, di-t-butylisopropylbismuth, diisopropyl-t-butylbismuth, di-t-butylneopentyl bismuth, dicyclohexylneopentyl bismuth, tris (4-methoxyphenyl) bismuth, tris (2-methylphenyl)

And tris (4-fluorophenyl)

Exemplary group 15 neutral electron donor ligands (ER) that have been provided for embodiments of the present invention₃). The scope of the invention is not limited to these exemplary ligands, however, it is believed that advantageous ER's can be understood from three general concepts₃Selection of the part. These three concepts are (1) ER₃Steric hindrance factor of (2) ER₃And (3) the metallation ability of the hydrocarbyl group.

The general Tolmanspatial arrangement model involves a cone angle θ (a measure of how filled the coordination sphere is with ligand), which typically ranges from 100 to 185 °. It is believed that the Tolman model (and the specific cone angles) apply equally to P, As, Sb, and Bi As effective ways to predict the catalytic activity of the compounds of formulae Ia and Ib. It is further believed that: for the embodiments of the present invention, ER₃Should be greater than 140 deg., it is advantageous for some embodiments to have a taper angle of 160 to 170 deg. and is particularly advantageous for other embodiments to have a taper angle of 170 deg. or higher. It should be noted that a cone angle of 180 ° indicates that the ligand effectively protects (or covers) half of the coordination sphere of the metal complex.

Looking again at the electronic considerations, it is believed that the electron donating ability (σ and π) of the ligands is related to the reactivity of the pro-initiators of formulas Ia and Ib. ER can be selected by various analytical methods₃The electronic properties of (a) a (b),these include the Tolman electronic parameters (X), ER₃The conjugate acid of (i.e. [ ER]₃H]⁺) pK of (2)_aValue, molecular calculation method such as minimum electrostatic potential (V) of molecule_{Minimum size}Quantitative measure of sigma-donating ability of E), calorimetric measurement of binding affinity, e.g. Ni (CO)₃+PR₃→Ni(CO)₃(PR₃) And standard reduction potential and corresponding electrochemical couple η -Cp (CO) (PR)₃)(COMe)Fe⁺/η-Cp(CO)(PR₃)(COMe)Fe⁰Enthalpy change. For example, for embodiments of the invention in which E ═ P, as measured by the Tolman electronic parameter (X), we believe it is appropriate to use its nickel complex lni (co)₃V is_C0Symmetry (A)₁) The frequency ofthe telescopic band is lower than 2068cm^-1ER of₃Fraction, this value is between 2060 and 2055cm^-1In the range of less than 2055cm, this value is advantageous^-1Is most advantageous. It is believed that other analytical methods either directly related to or proportional to the Tolman electronic parameter may be used to generate the pro-initiators and initiators of the present invention having the desired level of activity.

Removing ER₃In addition to predicting the combination of electronic and steric factors as a means of assessing catalytic activity, it is also believed that certain hydrocarbyl groups may be more susceptible to palladium-centered metallation than others, and that some of these hydrocarbyl groups may be more susceptible to β -hydride elimination than others₃Can control or at least tailor the metallization of the Pd center for a particular reaction activity and subsequent β -hydride elimination to produce a hydrogenated palladium initiator, for example, triisopropylphosphine is more favored than diisopropylmethylphosphine, which is more favored than isopropyldimethylphosphine.

In an embodiment of the present invention, E (R)₃It may be advantageous for some of the hydrogens of R (R ═ H or R ═ hydrocarbyl) to be replaced by deuterium. When hydrogen in reactant molecules is replaced by deuterium, the reactants are in the same environmentThe reaction rate is usually varied because more energy is required to completely dissociate deuterium than the corresponding hydrogen bond. This change is called the isotopic effect of deuterium and can be represented by k_h/k_dIs represented by a ratio, wherein k_hAnd k_dDissociation rate constants for hydrogen and deuterium, respectively. The effect of isotopic substitution is to reduce the rate of the heavier isotope reaction and hence the rate of palladium hydride/deuteride formation, since the bonds involved in the isotope in the step determining the rate of palladium hydride formation and the Pd-H bonds in the isotope exchange atoms are stronger in the initiator in the transition state of the polymerization. In one proposed non-limiting mechanism, the rate-determining step involves dissociation of carbon-hydrogen bonds, thus exhibiting a pronounced deuterium isotope effect, and the rate of polymerization, i.e., latency, will be improved since the rate of initiation relative to propagation is also slowed. The isotopic effect of deuterium is generally in the range of 1 (no isotopic effect) to about 8, although in some cases alreadyLarger or smaller values are reported. Thus, the use of this isotopic substitution can be used to improve reaction latency while maintaining the basic chemical nature (electronic configuration) and basic reactivity of the molecule.

As described herein, the term deuterium isotope effect means primary and secondary isotope effects; deuterium substitution of hydrogen adjacent to the C-H bond cleavage site can occur with induction latency, slowing the reaction. Tritium substitution of hydrogen produces even greater isotopic effects, and thus such tritium-substituted initiators will have longer latencies than deuterium-substituted initiators.

Deuteration E (R)₃Typical examples of (a) include fully deuterated and partially deuterated species. A typical deuteride is E (d)₇-C₃H₇)₃And E (d)₁₁-C₆H₁₁)₃(ii) a The partial deuteride is E (d)₁-C₃H₇)₃、E(d₁-C₆H₁₁)₃And E (d)₄-C₆H₁₁)₃Wherein E is selected from P, As, Sb, and Bi. The structural formula of a typical phosphorus-containing material is shown in the following structure a:

P(d₇-C₃H₇)₃P(d₆-C₃H₇)₃P(d₁-C₃H₇)₃

P(d₁₁-C₆H₁₁)₃P(d₄-C₆H₁₁)₃P(d₁-C₆H₁₁)₃(A)

referring again to formula Ia, where a is 2 and E is phosphorus, the two phosphine groups may together form a diphosphine chelating ligand. Typical diphosphine chelating ligands include, but are not limited to, bis (dicyclohexylphosphino) methane;

1, 2-bis (dicyclohexylphosphino) ethane;

1, 3-bis (dicyclohexylphosphino) propane;

1, 4-bis (dicyclohexylphosphino) butane;

1, 5-bis (dicyclohexylphosphino) pentane;

1, 2-bis (diisopropylphosphino) ethane;

1, 3-bis (diisopropylphosphino) propane; and

1, 4-bis (diisopropylphosphino) butane.

As previously described for formula Ia, Q is an anionic ligand selected from carboxylate, thiocarboxylate, and dithiocarboxylate groups. The ligand bound to the palladium metal center may be monodentate, symmetrically bidentate, asymmetrically chelated bidentate, asymmetrically bridged, or symmetrically bridged. Typical structural formulae include, but are not limited to, the following schematic structure B:

of symmetrical two teeth with a single tooth, of asymmetrical two teeth

Asymmetrically bridged B of asymmetric bidentate symmetry

Wherein X is independently oxygen or sulfur, R¹Selected from hydrogen, straight and branched C₁-C₂₀Alkyl radical, C₁-C₂₀Haloalkyl, substituted and unsubstituted C₃-C₁₂Cycloalkyl, substituted and unsubstituted C₂-C₁₂Alkenyl, substituted and unsubstituted C₃-C₁₂Cycloalkenyl, substituted and unsubstituted C₅-C₂₀Polycycloalkyl, substituted and unsubstituted C₆-C₁₄Aryl, and substituted and unsubstituted C₇-C₂₀An aralkyl group. The term haloalkyl, as used herein, means an alkyl group wherein at least one hydrogen atom is replaced with a halogen atom selected from the group consisting of fluorine, chlorine, bromine, iodine, and combinations thereof. The degree of halogenation can range from at least one hydrogen atom on the alkyl group being substituted with a halogen atom (e.g., monofluoromethyl) to complete halogenation (e.g., perhalogenation) in which all hydrogen atoms on the alkyl group are substituted with halogen atoms.

Substituted as used herein is understood to mean that the substituted group or substituent may contain one or more C groups selected from straight and branched chain₁-C₅Alkyl radical, C₆-C₁₄Aryl, and a moiety selected from the group consisting of fluorine, chlorine, bromine, iodine, and combinations thereof. The above-mentioned parts may also be substituted in the manner just described. Typical of R¹The group is methyl, trifluoromethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, neopentyl, cyclohexyl, norbornyl, adamantyl, phenyl, pentafluorophenyl, and benzyl. Advantageous exemplary anionic ligands include acetate (CH)₃CO₂ ^-) And Me₃CCO₂ ^-. Other typical anionic ligands include CF₃CO₂ ^-、C₆H₅CO₂ ^-、C₆H₅CH₂CO₂ ^-And C₆F₅CO₂ ^-. Still others include, but are not limited to, thioacetate (CH)₃C(S)O^-) Dithioacetate (CH)₃C(S)₂ ^-)、CF₃C(S)O^-、CF₃C(S)₂ ^-、Me₃CC(S)O^-、Me₃CC(S)₂ ^-、C₆H₅C(S)O^-、C₆H₅C(S)₂ ^-、C₆H₅CH₂(S)O^-、C₆H₅CH₂(S)₂ ^-、C₆F₅C(S)O^-And C₆F₅C(S)₂ ^-。

In both symmetric and asymmetric bridging embodiments according to the present invention, the palladium pre-initiator cation may be present in the form of a dimer. Typical structural formulas include, but are not limited to, the following schematic structure D:

in the above structure, R, E, LB is as previously defined for formula I, R¹And X is as defined for structure B.

The lewis base ligand according to the present invention may be any compound that provides an electron pair. Typical lewis bases are water or one of the following types of compounds: alkyl ethers,cyclic ethers, aliphatic or aromatic ketones, alcohols, amines, imines, amides, isocyanates, nitriles, isonitriles, cyclic amines, in particular pyridine and pyrazine, and trialkyl or triaryl phosphites.

More specifically, advantageous exemplary lewis base ligands include acetonitrile, pyridine, 2, 6-lutidine, 2, 6-dimethylpyrazine, and pyrazine. Other typical Lewis base ligands include water, dimethyl ether, diethyl ether, tetrahydrofuran, benzonitrile, tert-butyl nitrile, tert-butyl isocyanide, xylyl isocyanide, 4-dimethylaminopyridine, tetramethylpyridine, 4-methylpyridine, tetramethylpyrazine, triisopropyl phosphite, triphenyl phosphite, and triphenylphosphine oxide. Others include, but are not limited to, dioxane, acetone, benzophenone, acetophenone, methanol, isopropanol, triethylamine, dimethylaniline, N-neopentylidenemamine, 1-dimethyl-N-neopentylidenemethamine, N-methyltrimethylacetamide, N-methyl-cyclohexanamide, dimethylaminopyridine, tetramethylpyrazine, and triphenyl phosphite. As a typical Lewis base may also be included a phosphine, provided that it is added to the reaction medium during the formation of the one-component pro-initiator of the invention. Examples of lewis base phosphines include, but are not limited to, triisopropylphosphine, tricyclohexylphosphine, tricyclopentylphosphine, and triphenylphosphine.

Still with respect to formulas Ia and Ib, the WCA is selected from triflimide, borate and aluminate anions. When WCA is triflimide, it is represented by the following formula II:

N(S(O)₂R)₂ ^-II

in the case where the WCA is borate or aluminate, it is represented by the following formulas III and IV:

[M(R¹⁰)(R¹¹)(R¹²)(R¹³)]^-III

[M(OR¹⁴)(OR¹⁵)(OR¹⁶)(OR¹⁷)]^-IV

where formula II is recited previously, R is as defined above for formula Ia, and typical triflimides include, but are not limited to, bis (trifluoromethanesulfonyl) imide, triflimide ([ N (S (O))₂C₄F₉)₂]^-) Bis (pentafluoroethanesulfonyl) imide group ([ N (S (O))₂C₂F₅)₂]^-) And 1, 1, 2, 2, 2-pentafluoroethane-N- [ (trifluoromethyl) sulfonyl group]Sulfonamide radical ([ N (S (O))₂CF₃)(S(O)₂C₄F₉)]^-). Alternatively, the WCA can be the tris (trifluoromethanesulfonyl) methane anion ([ C (S (O))₂CF₃)₃]^-)。

Further of the formula III, M is boron or aluminum, R¹⁰、R¹¹、R¹²And R¹³Independently of each otherRepresents fluorine, straight-chain and branched C₁-C₁₀Alkyl, straight and branched C₁-C₁₀Alkoxy, straight and branched C₃-C₅Haloalkenyl, straight and branched C₃-C₁₂Trialkylsiloxy radical, C₁₈-C₃₆Triarylsiloxy, substituted and unsubstituted C₆-C₃₀Aryl, and substituted and unsubstituted C₆-C₃₀Aryloxy group, wherein R¹⁰To R¹³And not both alkoxy or aryloxy. R¹⁰To R¹³Selected from substituted aryl or aryloxy groups, which groups may be mono-or polysubstituted, wherein the substituents are independently selected from straight-chain and branched C₁-C₅Alkyl, straight and branched C₁-C₅Haloalkyl, straight and branched C₁-C₅Alkoxy, straight and branched C₁-C₅Haloalkoxy, straight and branched C₁-C₁₂Trialkylsilyl group, C₆-C₁₈Triarylsilyl groups, and a halogen selected from chlorine, bromine, iodine, and fluorine.

Advantageous exemplary borate anions include tetrakis (pentafluorophenyl) borate and tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate. Other typical borate anions include tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate, tetrakis (3, 4, 5, 6-tetrafluorophenyl) borate, tetrakis (1, 2, 2-trifluorovinyl) borate, tetrakis (4-triisopropylsilyltetrafluorophenyl) borate, tetrakis (4-dimethyl-tert-butylsilyltetrafluorophenyl) borate, (tetrakis [3, 5-bis [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl]phenyl) borate, tetrakis [3- [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl]-5- (trifluoromethyl) phenyl]borate, and tetrakis [3- [2, 2, 2-trifluoro-1- (2, 2, 2-trifluoroethoxy) -1- (trifluoromethyl) ethyl]-5- (trifluoromethyl) phenyl]borate.

Other borate anions include, but are not limited to, tetrakis (2-fluorophenyl) borate, tetrakis (3-fluorophenyl) borate, tetrakis (4-fluorophenyl) borate, tetrakis (3, 5-difluorophenyl) borate, tetrakis (3, 4, 5-trifluorophenyl) borate, methyltris (perfluorophenyl) borate, ethyltris (perfluorophenyl) borate, phenyltris (perfluorophenyl) borate, (triphenylsiloxy) tris (pentafluorophenyl) borate, (octyloxy) tris (pentafluorophenyl) borate, tetrakis [3, 5-bis [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl]phenyl]borate, and tetrakis [3- [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl]-5- (trifluoromethyl) phenyl]borate.

Advantageous typical aluminate anions encompassed by formula III are tetrakis (pentafluorophenyl) aluminate and tetrakis (3, 5-bis (trifluoromethyl) phenyl) aluminate. Other typical aluminate anions include, but are not limited to, tris (perfluorobiphenyl) fluoroaluminate, (octyloxy) tris (pentafluorophenyl) aluminate, and methyltris (pentafluorophenyl) aluminate.

Further of the formula IV, M is boron or aluminum, R¹⁴、R¹⁵、R¹⁶And R¹⁷Independently represent straight-chain and branched C₁-C₁₀Alkyl, straight and branched C₁-C₁₀Haloalkyl, C₂-C₁₀Haloalkenyl, substituted and unsubstituted C₆-C₃₀Aryl, and substituted and unsubstituted C₇-C₃₀Aralkyl radical, with the proviso that R¹⁴To R¹⁷At least three of which must contain halogen-containing substituents. R¹⁴To R¹⁷Selected from substituted aryl or aryloxy groups, which groups may be mono-or polysubstituted, wherein the substituents are independently selected from straight-chain and branched C₁-C₅Alkyl, straight and branched C₁-C₅Haloalkyl, straight and branched C₁-C₅Alkoxy, straight and branched C₁-C₁₀Haloalkoxy, and halogen selected from chlorine, bromine, and fluorine. OR (OR)¹⁴And OR¹⁵The radicals may be taken together to form-O-R¹⁸A chelating substituent represented by-O-, wherein the oxygen atom is bonded to M, and R¹⁸Is selected from substituted and unsubstituted C₆-C₃₀Aryl and substituted and unsubstituted C₇-C₃₀A divalent radical of an aralkyl group. In one embodiment of the invention, the oxygen atom is bonded to the aromatic ring directly or via an alkyl group in the ortho or meta position. When substituted, theThe aryl and aralkoxy groups may be mono-or polysubstituted, wherein the substituents are independently selected from the group consisting of straight and branched C₁-C₅Alkyl, straight and branched C₁-C₅Haloalkyl, straight and branched C₁-C₅Alkoxy, straight and branched C₁-C₁₀Haloalkoxy, and halogen selected from chlorine, bromine,and fluorine.

Divalent R¹⁸A typical structure of the radical is shown in Structure E below:

wherein R is¹⁹Independently represent hydrogen, straight and branched C₁-C₅Alkyl, straight and branched C₁-C₅Haloalkyl, and halogen selected from chlorine, bromine, and fluorine; r²⁰May be a single substituent or up to four per aromatic ring, and independently represent hydrogen, straight and branched chain C, depending on the valences available on each ring carbon atom₁-C₅Alkyl, straight and branched C₁-C₅Haloalkyl, straight and branched C₁-C₅Alkoxy, straight and branched C₁-C₁₀Haloalkoxy, and halogen selected from chlorine, bromine, and fluorine; and s independently represents an integer of 0 to 6. It will be appreciated that when s is 0, then the formula-O-R¹⁸The oxygen atom in-O-being directly bound to R¹⁸The carbon atoms in the aromatic ring shown are bonded. In the above divalent structural formula, an oxygen atom (i.e., when s is 0) and a methylene group or a substituted methylene group- (C (R)¹⁹)₂)_sFavouring the ortho or meta position on the aromatic ring. Typical formula-O-R¹⁸Chelating groups for-O-include, but are not limited to, 2, 3, 4, 5-tetrafluorobenzenediolato (-OC)₆F₄O-), 2, 3, 4, 5-tetrachlorobenzenediol (-OC)₆Cl₄O-), 2, 3, 4, 5-tetrabromobenzene diphenol radical (-O)₆Br₄O-), and bis (1, 1 '-bis (tetrafluorophenyl) -2, 2' -diphenol).

Advantageous exemplary aluminate anions include [ Al (OC (CF)]₃)₂Ph)₄]^-、[Al(OC(CF₃)₂C₆H₄CH₃)₄]^-、[Al(OC(CF₃)₂C₆H₄-4-t-Bu)₄]^-、[Al(OC(CF₃)₂C₆H₃-3，5-(CF₃)₂)₄]^-、[Al(OC(CF₃)₂C₆H₂-2，4，6-(CF₃)₃)₄]^-And [ Al (OC (CF)]₃)₂C₆F₅)₄]^-. Typical borate and aluminate anions include, but are not limited to, [ Al (OC (CF)₃)₃)₄]^-Bis [3, 4, 5, 6-tetrafluoro-1, 2-benzenediol group-. kappa.O,. kappa.O']Borate ([ B (O)]₂C₆F₄)₂]^-)、[B(OC(CF₃)₃)₄]^-、[B(OC(CF₃)₂(CH₃))₄]^-、[B(OC(CF₃)₂H)₄]^-、[B(OC(CF₃)(CH₃)H)₄]^-、[B(O₂C₆F₄)₂]^-、[B(OCH₂(CF₃)₂)₄]^-、[Al(OC(CF₃)₃)₄]^-、[Al(OC(CF₃)(CH₃)H)₄]^-、[Al(OC(CF₃)₂H)₄]^-、[Al(OC(CF₃)₂C₆H₄-4-i-Pr)₄]^-、[Al(OC(CF₃)₂C₆H₄-4-SiMe₃)₄]^-、[Al(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄]^-And [ Al (OC (CF)]₃)₂C₆H₂-2，6-(CF₃)₂-4-Si-i-Pr₃)₄]^-。

Pyrolysis of Palladium Pre-initiator

Production of active intermediates and palladium hydrides

Referring to FIG. 1, a hypothetical mechanism for forming various triisopropylphosphine derivatives (A, B, C, D, E, F, G, H and I) of the present invention is shown. The one-component photoinitiator B is shown to be a palladium complex A containing a group 15 electron donor ligand, triisopropylphosphine, and an acetate ligand with the WCA salt LiFeABA etherate ([ Li (OEt)₂)_2.5][FABA]) And lewis base acetonitrile. The one-component pro-initiator C is shown to be the result of the reaction of the palladium complex A with DANFABA. Thus, the pre-initiator B is obtained in the presence of a Lewis base and the pre-initiator C is obtained in the absence of a Lewis base. It is also believed that the protomonodentate carboxylate ligand B converts to the kappa (bidentate) configuration of C upon loss of Lewis base upon heating. It is believed that both pre-initiator embodiments B and C are separable and both exhibit latent polymerization activity. Alternatively, as shown in FIG. 1, the pro-initiator complex C may also be obtained by: the palladium complex a is reacted with p-toluenesulfonic acid to form complex H in situ, wherein the acetate ligand is replaced by a tosylate anion. Then, when the complex H reacts with LiFeABA etherate, a pre-initiator C is obtained.

It is believed that the pre-initiator C generates the ligand metallated species D by losing acetic acid conversion under pyrolytical conditions, as shown. It is believed that the metalating species D may also be isolated and converted under appropriate activation conditions, i.e., heating, to the hydride-acetonitrile-trialkylphosphine-dialkylalkenylphosphinepalladium, believed to be the cationic palladium hydride initiator complex, designated as E in figure 1. Initiator complex E undergoes disproportionation which is believed to result in the competition of two types (saturated and unsaturated) of phosphine species at the metal center to produce three cationic palladium hydride complex derivatives, proto-complex E and species F and G, as shown.

Alternatively, it is believed that in the presence of an appropriate activation temperature and lewis base, the pro-initiator B may undergo a pyrolysis reaction in which the carboxylate anion decarboxylates (i.e., loses CO)₂) Formation of active hydrocarbyl palladium (e.g. R)¹Methyl) catalyst species, as represented by I in figure 1. It is also believed that the active catalyst species I can undergo further pyrolytic rearrangement to lose the hydrocarbyl ligand (e.g., methane) to produce an active hydride initiator (not shown). Furthermore, it is also believed that under certain reaction conditions, the substances I can pass throughThe field formed acetic acid protonates the methyl palladium functionality and rejoins the hydride forming sequence to produce the pro-initiator C.

Preparation of palladium initiator complexes

Palladium complexes containing group 15 electron donor ligands are commercially available or may be synthesized by well-known synthetic routes. In a synthetic route, the general formula is Pd (Q)₂With a palladium compound of the formula E (R)₃In an inert solvent at a suitable temperature to form a compound of the formula Pd (Q)₂(E(R)₃)₂Wherein Q, E and R are as previously defined for formula Ia. Typical formula Pd (Q)₂(E(R)₃)₂Is selected from, but not limited to, Pd (OAc)₂(P(i-Pr)₃)₂、Pd(OAc)₂(P(Cy)₃)₂、Pd(O₂C-t-Bu)₂(P(Cy)₃)₂、Pd(OAc)₂(P(Cp)₃)₂、Pd(O₂CCF₃)₂(P(Cy)₃)₂、Pd(O₂CPh)₂(PCy₃)₂、Pd(OAc)₂(As(i-Pr)₃)₂And Pd (OAc)₂(As(Cy)₃)₂. In addition, Pd (OAc)₂(Sb(Cy)₃)₂. A typical reaction scheme for this synthetic route is shown below:

wherein R is as defined for formula Ia, X and R¹As defined for structure B.

The reaction formula is shown below as Pd (Q)₂Wherein Q is acetate and the group 15 ligand is triisopropylphosphine (P-i-Pr)₃)。

Pd(Q)₂Is Pd (OAc)₂In the case of (2), they are generally commercially available. Other palladium carboxylates, palladium thioacetate, and palladium dithioacetate may not be readily available. Advantageously, these other carboxylates, thioacetates and dithioacetates readily pass through Pd (OAc)₂With at least two equivalents of a suitable carboxylic acid (R)¹CO₂H) Thiocarboxylic acid (R)¹C (S) OH) or dithiocarboxylic acid (R)¹CS₂H) And (3) reaction preparation. For purposes of illustration, the reaction is generally represented as follows:

Pd(O₂CCH₃)₂+2HO₂CR¹→Pd(O₂CR¹)₂+2HO₂CCH₃

more specifically, the following is exemplified:

Pd(O₂CCH₃)₂+2HO₂CCMe₃→Pd(O₂CCH₃)₂+2HO₂CCMe₃

more generally, the one-component pro-initiators of formula Ia may be prepared by: mixing a palladium complex precursor with a salt of a weakly coordinating anion in a suitable solvent at asuitable reaction temperature(e.g., -78 to 25 ℃) to completion and then isolating the pro-initiator product. In one embodiment of the invention, a compound of the formula [ Pd (E (R))₃)_a(Q)₂]_pWith a WCA salt in an inert solvent in the absence of a Lewis base to give a compound of the formula [ Pd (kappa.)]²-Q)(E(R)₃)_a]_p[WCA]_rWherein Q, E, R, a, p and R are as previously defined for formula Ia. [ Pd (Q)₂(E(R)₃)_a]_pWhen reacted with WCA salts in the absence of Lewis bases or very poorly coordinating Lewis bases (i.e., readily displaced from the metal center by the oxygen or sulfur of acetate, thioacetate or dithioacetate), the anionic ligand contained in the palladium complex precursor is converted from a monodentate configuration to a bidentate or kappa in the resulting pro-initiator product²-configuration. A typical reaction for this embodiment is as follows:

the following typical reaction formula includes Pd (P- (i-Pr)₃))₂(O₂CCH₃)₂A raw material, theThe salt of the weakly coordinating anion used in the conversion is N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (DANBABA).

In another embodiment of the invention, the palladium compound is prepared by isomerizing a palladium compound of formula Ib ([ (E (R))₃)(E(R)₂R*)Pd(LB)]_p[WCA]_r) Reaction with carboxylic, thiocarboxylic or dithiocarboxylic acids to give the proinitiator [ Pd (. kappa.)]²-Q)(E(R)₃)_a]_p[WCA]_r(C in FIG. 1). Wherein R and R are aspreviously defined for formulae Ia and Ib, as shown below:

substance [ Pd (LB) (ER)₃)(ER₂R*)][WCA]Is selected from

[Pd(P-(i-Pr)₃)(κ²-P，C-P(-i-Pr)₂(C(CH₃)₂) (acetonitrile)) [ B (C)₆F₅)₄]、

[Pd(P-(i-Pr)₃)(κ²-P，C-P(-i-Pr)₂(C(CH₃)₂) (pyrazine)) [ B (C)₆F₅)₄]、

[Pd(P-(i-Pr)₃)(κ²-P，C-P(-i-Pr)₂(C(CH₃)₂) (pyridine)][B(C₆F₅)₄]、

[Pd(κ²-P，C-PCy₂(C₆H₁₀) (acetonitrile)][B(C₆F₅)₄]、

[Pd(κ²-P，C-PCy₂(C₆H₁₀) - (pyrazine)][B(C₆F₅)₄]And, and

[Pd(κ²-P，C-PCy₂(C₆H₁₀) (pyridine)][B(C₆F₅)₄]。

Furthermore, the relevant metallized deuterides [ Pd (P (C)₃D₇)₃)(κ²-P，C-P(i-C₃D₇)₂(C(CD₃)₂) (acetonitrile)][B(C₆F₅)₄]And [ Pd (P (C)]₆D₁₁)₃)(κ²-P，C-P(C₆D₁₁)₂(C₆D₁₀) (acetonitrile)][B(C₆F₅)₄]But also applicable.

The carboxylic, thiocarboxylic or dithiocarboxylic acid is selected from acetic acid, trifluoroacetic acid, pivalic acid (Me)₃CCO₂H) Thioacetic acid (CH)₃C (S) OH), benzoic acid (C)₆H₅CO₂H) Thiobenzoic acid (C)₆H₅C (S) OH), pentafluorobenzoic acid (C)₆F₅CO₂H) Trifluoro-methyl benzoic acid (4-CF)₃C₆H₄CO₂H) And 4-methoxybenzoic acid (4-CH)₃OC₆H₄CO₂H) And the forms in which the hydrogen on the acid is replaced by deuterium.

This embodiment of the invention is illustrated in the following reaction scheme, in which the substance [ Pd (LB) (ER)₃)(ER₂R*)][WCA]Protonation by organic acids to give kappa²-derivative [ Pd (ER)₃)₂(Q)][WCA]：

Representative [ Pd (LB) (ER) based on isopropyl and cyclohexyl groups₃)(ER₂R*)][WCA]The substances are:

the following reaction scheme illustrates an advantageous embodiment of the invention:

in another embodiment of the present invention, formula (Pd (Q))₂(E(R)₃)_a)_p(see FIG. 1B) a palladium complex containing a group 15 electron donor ligand is reacted simultaneously with a WCA salt and a Lewis base in a suitable solvent to provide a palladium pro-initiator of formula Ia. Can make lewisThe base is dissolved in the reaction solvent or a Lewis base may be used as the reaction solvent. An exemplary reaction is as follows:

the following exemplary reaction scheme is for Pd (P-i-Pr) as the starting material₃)₂(O₂CCH₃)₂The Lewis base is acetonitrile and the salt of the weakly coordinating anion is tetrakis (pentafluorophenyl) borate (diethyl ether)_2.5Lithium complex (Li (OEt)₂)_2.5FABA).

Other LB ligand substituted pro-initiator species according to the present invention may be produced by reacting the resulting LB ligand substituted pro-initiator with a lewis base that binds more strongly than the substituted LB ligand.

In the embodiment of the non-lewis base coordinated pro-initiator of the present invention, the synthesis reaction is carried out in an inert solvent. The reaction involves dissolving the selected group 15 complex palladium compound in an inert solvent and then adding the selected WCA salt to the solution in an equivalent of 1: 1. Examples of suitable inert solvents include, but are not limited to, alkane and cycloalkane solvents such as pentane, hexane, heptane and cyclohexane; halogenated alkane solvents such as dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1-dichloroethane, 1, 2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, and 1-chloropentane; aromatic solvents such as benzene, xylene, toluene, anisole, 1, 3, 5-trimethylbenzene, chlorobenzene, o-dichlorobenzene, and fluorobenzene; and halocarbon solvents such as Freon 112(DuPont Corporation, Wilimngton, DE); and mixtures thereof. Under certain experimental circumstances and certain palladium initiator generation, the use of certain ethers such as diethyl ether, dimethyl ether, dioxane, and tetrahydrofuran mayform a pro-initiator embodiment that is free of lewis bases, although such ethers are generally considered lewis bases.

In connection with the embodiment of the Lewis base coordinated pre-initiator according to the invention, the synthesis reaction with the WCA salt can be carried out in the presence of the inert solvents listed above or in the pure state in the case where the Lewis base chosen is also a solvent. Typical lewis base solvents are dimethyl ether, diethyl ether, dioxane, acetonitrile, tetrahydrofuran, pyridine, benzonitrile, and trialkylphosphines, including trimethylphosphine, triisopropylphosphine, and tricyclohexylphosphine.

In the case where the synthesis of the LB coordinated pro-initiator is carried out in an inert solvent, the group 15 coordinated palladium compound is first dissolved in the solvent, and then the desired Lewis base and WCA salt are added to the solution in an equivalent ratio of 1: 1 to 1: 1.5 (palladium compound: Lewis base: WCA salt). In this inert solvent, the lewis base coordinates to the palladium as a LB ligand. As previously mentioned, the phosphine is considered to be a Lewis base when it is added during the formation of the pre-initiator (i.e., when it is added during the reaction of the group 15 ligated palladium compound with the WCA salt). In the case where the Lewis base is a solvent, the group 15 coordinated palladium compound and WCA salt are added to the Lewis base in an equivalent ratio of 1: 1 (palladium compound: WCA salt); there is of course an excess of lewis base solvent.

In another embodiment of the invention, the metal compound is prepared by reacting a palladium (Pd) (LB) (ER) metal compound of formula Ib₃)(ER₂R*)][WCA](see D in FIG. 1) is heated (or otherwise energized) to produce an initiator [ (ER)₃)₂Pd(H)(LB)][FABA](see E, F and G in FIG. 1).

The following reaction scheme illustrates this embodiment.

More specifically, for the embodiment of triisopropylphosphine

Embodiments for the Tricyclohexylphosphine derivative

In summary, embodiments according to the invention include the following advantageous compounds of formulae Ia and Ib:

[Pd(OAc)(P(Cy)₃)₂(MeCN)][B(C₆F₅)₄]、

[Pd(OAc)(P(Cy)₂(CMe₃))₂(MeCN)][B(C₆F₅)₄]、

[Pd(OAc)(P(i-Pr)(CMe₃)₂)₂(MeCN)][B(C₆F₅)₄]、

[Pd(OAc)₂(P(i-Pr)₂(CMe₃))₂(MeCN)][B(C₆F₅)₄]、

[Pd(OAc)(P(i-Pr)₃)₂(MeCN)][B(C₆F₅)₄]、

[Pd(O₂C-t-Bu)(P(Cy)₃)₂(MeCN)][B(C₆F₅)₄]、

[Pd(O₂C-t-Bu)(P(Cy)₂(CMe₃))₂(MeCN)][B(C₆F₅)₄]、

[Pd(O₂C-t-Bu)₂(P(i-Pr)₂(CMe₃))₂、

[Pd(O₂C-t-Bu)(P(i-Pr)₃)₂(MeCN)][B(C₆F₅)₄]、

cis-[Pd(P(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(MeCN))[B(C₆F₅)₄]and, and

cis-[Pd(P(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(NC₅H₅)][B(C₆F₅)₄]。

other advantageous examples of compounds of formulae Ia and Ib include [ Pd (OAc)) (P (Cp)₃)₂(MeCN)][B(C₆F₅)₄]、[Pd(OAc)(P(i-Pr)₂(CMe₃))₂(MeCN)][B(C₆F₅)₄]、[Pd(O₂C-t-Bu)(P(Cp)₃)₂(MeCN)][B(C₆F₅)₄]、[Pd(O₂C-t-Bu₂(P(i-Pr)(CMe₃)₂)(MeCN)][B(C₆F₅)₄]、[Pd(O₂C-t-Bu)(P(i-Pr)₂(CMe₃))₂(MeCN)][B(C₆F₅)₄]、cis-[Pd(P(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(NC₅H₅)][B(C₆F₅)₄]、cis-[Pd(P(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(2，6-Me₂py)][B(C₆F₅)₄]And cis- [ Pd (P (i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(2，6-Me₂pyz)][B(C₆F₅)₄]。

Still other examples of compounds of formula Ia and Ib include, but are not limited to, [ (P (Cy))₃)₂Pd(κ²-O，O’-O₂CCH₃)][B(C₆F₅)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂C-t-Bu)][B(C₆F₅)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂CC₆H₅)][B(C₆F₅)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂CC₆F₅)][B(C₆F₅)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂CCF₃)][B(C₆F₅)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂CCH₃)][B(C₆H₃-3，5-(CF₃)₂)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂CCH₃)][Al(OC(CF₃)₂C₆H₄CH₃)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂CPh)][B(C₆F₅)₄]、[(P(Cy-d₁₁)₃)₂Pd(κ²-O，O-OAc)][B(C₆F₅)₄]、[Pd(P(i-Pr)₃)₂(κ²-O，O’-O₂CCH₃)][B(C₆F₅)₄]、[Pd(P(i-Pr)₃)₂(κ²-O，O’-O₂C-t-Bu)][B(C₆F₅)₄]、[(P(i-Pr)₃)₂Pd(κ²-O，O-O₂CCF₃)][B(C₆F₅)₄]、[(P(i-Pr)₃)₂Pd(κ²-O，O-O₂CC₆F₅)][B(C₆F₅)₄]、[(P(i-Pr)₃)₂Pd(κ²-O，O-O₂CC₆H₅)][B(C₆F₅)₄]、[(P(i-Pr)₃)₂Pd(κ²-O，O-O₂CC₆H₄-p-(CF₃))][B(C₆F₅)₄]、[(P(i-Pr)₃)₂Pd(κ²-O，O-O₂CC₆H₄)-p-(OMe)][B(C₆F₅)₄]、[Pd(P(Cy)₂(CMe₃))₂(κ²-O，O-O₂CCH₃)][B(C₆F₅)₄]、[Pd(P(Cy)(CMe₃)₂)₂(κ²-O，O’-O₂CCH₃)][B(C₆F₅)₄]、[Pd(P(i-Pr)₂(CMe₃))₂(κ²-O，O’-O₂CCH₃)][B(C₆F₅)₄]、[Pd(P(i-Pr)(CMe₃)₂)₂(κ²-O，O’-O₂CCH₃)][B(C₆F₅)₄]、[Pd(κ²-O，O’-OAc)(As(Cy)₃)₂][B(C₆F₅)₄]、[Pd(κ²-O，O’-OAc)(As(i-Pr)₃)₂][B(C₆F₅)₄]、[Pd(As-i-Pr₃)₂(O₂CCH₃)(NCCH₃)][B(C₆F₅)₄]、[Pd(As(Cy)₃)₂(O₂CCH₃)(NCCH₃)][B(C₆F₅)₄]、[(P(Cy-d₁₁)₃)₂Pd(NCMe)(O₂CCH₃)][B(C₆F₅)₄]、[(P(Cy-d₁)₃)₂Pd(NCMe)(O₂CCH₃)][B(C₆F₅)₄]、[Pd(O₂CCH₃)(P(Cy)₃)₂(MeCN)][B(C₆F₅)₄]、[Pd(O₂CCH₃)(P(i-Pr)₃)₂(MeCN)][B(C₆F₅)₄]、[Pd(O₂CCH₃)(P(i-Pr)₃)₂(MeCN)][B(C₆H₃-3，5-(CF₃)₂)₄]、[Pd(O₂CCH₃)(P(Cy)₃)₂(MeCN)][Al(OC(CF₃)₂C₆H₄CH₃)₄]、[Pd(O₂CCH₃)(P(i-Pr)₃)₂(MeCN)][Al(OC(CF₃)₂C₆H₄CH₃)₄]、[Pd(O₂C-t-Bu)](P(Cy)₃)₂(MeCN)[B(C₆F₅)₄]、[Pd(O₂CPh)(P(Cy)₃)₂(NCMe)][B(C₆F₅)₄]、[Pd(O₂CCF₃)(P(Cy)₃)₂(MeCN)][B(C₆F₅)₄]、[Pd(OAc)(P(Cy)₃)₂(NC₅H₅)][B(C₆F₅)₄]、[(P-i-Pr₃)₂Pd(O₂CCH₃)(NC₅H₅)][B(C₆F₅)₄]、[(P(Cy-d₁)₃)₂Pd(NCMe)(O₂CCH₃)][B(C₆F₅)₄]、[Pd(P(Cy)₃)₂(O₂CCH₃)(4-Me₂NC₅H₄N)][B(C₆F₅)₄]、[Pd(P(Cy)₃)₂(O₂CCH₃)(CNC₆H₃Me₂-2，6)][B(C₆F₅)₄]、trans-[(P-i-Pr₃)₂Pd(O₂CCH₃)(CNC₆H₃Me₂-2，6)][B(C₆F₅)₄]、[(PCy₂-t-Bu)₂Pd(O₂CCH₃)(MeCN)]B(C₆F₅)₄、[Pd(P(i-Pr)₂(CMe₃))₂(O₂CCH₃)(MeCN)][B(C₆F₅)₄]、[Pd(PCy₂-t-Bu)₂(O₂CCH₃)(MeCN)]B(C₆F₅)₄、cis-[Pd(P(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(NC₅H₅)][B(C₆F₅)₄]、cis-[Pd(P(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(2，6-Me₂py)][B(C₆F₅)₄]、cis-[Pd(P(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(2，6-Me₂pyz))[B(C₆F₅)₄]、cis-[Pd(P(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂))(4-t-BuC₅H₄N))[B(C₆F₅)₄]、[Pd(κ²-P，C-PCy₂(C₆H₁₀) (acetonitrile)][B(C₆F₅)₄]、[Pd(P(Cy)₃)(κ²-P，C-PCy₂(C₆H₁₀) - (pyrazine)][B(C₆F₅)₄]And [ PdP (Cy)]₃(κ²-P，C-PCy₂(C₆H₁₀) (pyridine)][B(C₆F₅)₄]。

Preparation of hydrogenated palladium derivatives by pyrolytic and synthetic routes

In one embodiment of the invention, the ligand may be activated by a carboxylate ligand [ ((R)₃E)_aPd(Q)(LB)_b]_p[WCA]_rDecarboxylation (loss of carbon dioxide (CO)₂) And elimination of small molecules (alkenes or alkanes), i.e., loss of isobutene, under the pyrolysis reaction conditions produces palladium hydride.

One embodiment is a substance [ ((R)₃E)_aPd(O₂CMe₃)(LB)_b]_p[WCA]_rMore specifically [ Pd (O)]₂C-t-Bu)(NCCH₃)(P(Cy)₃)₂][B(C₆F₅)₄]And [ Pd (O)₂C-t-Bu)(NCCH₃)(P(i-Pr)₃)₂][B(C₆F₅)₄]。

In one embodiment of the invention, the ligand may be activated by a carboxylate ligand [ ((R)₃E)_aPd(Q)(LB)_b]_p[WCA]_rDecarboxylation and elimination of small molecules (alkenes or alkanes) under pyrolysis reaction conditions produces palladium hydride.

In one embodiment of the invention, a strong acid (H) that passes directly through the WCA is favored⁺Or D⁺) Namely H (OEt)₂)_2.5[B(C₆F₅)₄]、[HNMe₂Ph][B(C₆F₅)₄](DANFEABA), or [ DNMe]₂Ph][B(C₆F₅)₄]In the presence of a suitable Lewis base (e.g. CH)₃CN) to a palladium (O) species to produce a hydrogenated or deuterated palladium initiator [ Pd (PR)₃)₂(H)(LB)][FABA]Producing the cationic hydride or deuteride of the invention.

Typical Pd (O) species include, but are not limited to, Pd (ER)₃)_nWherein n is 2, 3 or 4; pd₂(dba)₃. Selected substances include, but are not limited to, Pd₂(dba)₃、Pd(PPh₃)₄Pd (P (o-tolyl radical)₃)₄、Pd(P-i-Pr₃)₂、Pd(P-i-Pr₃)₃And Pd (PCy)₃)₂. The lewis base may be selected from any lewis base defined for the pro-initiator described in formula I.

WCA salt

In certain embodiments of the present invention, the salt of the weakly coordinating anion used in preparing the pre-initiator may be of the formula [ C]_e[WCA]_dWherein C represents a proton (H)⁺) An anion containing an organic group, or a cation of an alkali metal, alkaline earth metal or transition metal, WCA being as defined above, e and d representing the multiples of the cation complex (C) and weakly coordinating anion complex (WCA) employed to balance the charge on the total salt complex, respectively.

The alkali metal cation comprises a group 1 metal selected from lithium, sodium, potassium, rubidium, and cesium. The alkaline earth metal cation comprises a group 2 metal selected from beryllium, magnesium, calcium, strontium, and barium. The transition metal cation is selected from zinc, silver and thallium.

The organic radical cation is selected from the group consisting of ammonium, phosphonium, carbocations and silylium, i.e. [ NH (R)³⁰)₃]⁺、[N(R³⁰⁺⁾ ₄]⁺、[PH(R³⁰)₃]⁺、[P(R³⁰)₄]⁺、[(R³⁰)₃C]⁺And [ (R)³⁰)₃Si]⁺Wherein R is³⁰Independently represents a hydrocarbon group, a silylhydrocarbon group, or a perfluorohydrocarbon group, each of which has 1 to 24 carbon atoms and is arranged in a linear, branched, or cyclic structure. Perfluoroalkyl means that all carbons bonded to a hydrogen atom are substituted with a fluorine atom. Typical hydrocarbyl groups include, but are not limited to, straight and branched chain C₁-C₂₀Alkyl radical, C₃-C₂₀Cycloalkyl, straight and branched C₂-C₂₀Alkenyl radical, C₃-C₂₀Cycloalkenyl radical, C₆-C₂₄Aryl, and C₇-C₂₄Aralkyl groups, and organometallic cations. The organic cation is selected from the group consisting of trityl, trimethylsilyl, triethylsilyl, tris (trimethylsilyl) silyl, tribenzylsilyl, triphenylsilyl, tricyclohexylsilyl, dimethyloctadecylsilyl, and triphenylcarbenium (i.e., triphenylsilyl)Methyl group). Ferrocenium cations such as [ (C) in addition to the above-mentioned cationic complexes₅H₅)₂Fe]⁺And [ (C)₅(CH₃)₅)₂Fe]⁺It is also suitable as a cation in the WCA salt of the invention.

Advantageous WCA salts with weakly coordinating anions (as described in formulas II, III and IV) include tetra(pentafluorophenyl) boronic acid (etherate)_2.5Lithium (LiFeABA etherate), dimethylanilinium tetrakis (pentafluorophenyl) borate (DANBABA), and sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate. Other advantageous WCA salts include lithium trilimide or Li [ N (SO)₂C₄F₉)₂]Lithium bis (pentafluoroethanesulfonyl) imido [ LiN (SO)₂C₂F₅)₂](ii) a 1, 1, 2, 2, 2-pentafluoroethane-N- [ (trifluoromethyl) sulfonyl group]Lithium sulfonamido [ N (SO)₂CF₃)(SO₂C₄F₉)]Tris (trifluoromethanesulfonyl) methyllithium anion (Li [ C (SO)₂CF₃)₃])、Li[Al(OC(CF₃)₂Ph)₄]And Li [ Al (OC (CF)])₃)₂C₆H₄CH₃)₄]。

Other suitable WCA salts according to embodiments of the present invention include, but are not limited to, lithium bis (trifluoromethylsulfonyl) imide, lithium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, lithium tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate, lithium tetrakis (pentafluorophenoxy) borate, lithium tetrakis (3, 4, 5, 6-tetrafluorophenyl) borate, lithium tetrakis (1, 2, 2-trifluorovinyl) borate, lithium tetrakis (4-triisopropylsilyltetrafluorophenyl) borate, lithium tetrakis (4-dimethyl-tert-butylsilyltetrafluorophenyl) borate, lithium tetrakis [3, 5-bis (1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl) borate]Phenyl radical]Lithium borate, tetrakis [3- [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl group]-5- (trifluoromethyl) phenyl]Lithium borate, tetrakis [3- (2, 2, 2-trifluoro-1- (2, 2, 2-trifluoroethoxy) -1- (trifluoromethyl) ethyl]-5- (trifluoromethyl) phenyl]Lithium borate, lithium tetrakis (pentafluorophenyl) aluminate, lithium tris (perfluorobiphenyl) fluoroaluminate, and (octyloxy) tris (pentafluorobenzeneAlkyl) lithium aluminate, lithium tetrakis (3, 5-bis (trifluoromethyl) phenyl) aluminate, lithium methyltris (pentafluorophenyl) aluminate, bis [3, 4, 5, 6-tetrafluoro-1, 2-benzenediol-yl-. kappa.O,. kappa.O']Lithium borate (Li [ B (O)]₂C₆F₄)₂]) Dimethylanilinium tetrakis (pentafluorophenyl) borate ([ HNMe]₂Ph][B(OC₆F₅)₄]) Trimethylammonium tetrakis (pentafluorophenyl) borate ([ HNMe)₃][B(OC₆F₅)₄])、Li[Al(OC(CF₃)₂Ph)₄]、Li[Al(OC(CF₃)₂C₆H₄CH₃)₄、Li[Al(OC(CF₃)₂C₆H₄-4-t-Bu)₄]、Li[Al(OC(CF₃)₂C₆H₃-3，5-(CF₃)₂)₄]、Li[Al(OC(CF₃)₂C₆H₂-2，4，6-(CF₃)₃)₄]^-And Li [ Al (OC (CF)])₃)₂C₆F₅)₄]^-。

Monomer

The pro-initiators of the present invention are useful in the preparation of a variety of polymers containing cyclic repeat units. Polycyclic olefin monomers are polyaddition polymerized in the presence of catalytic amounts of a one-component photoinitiator of formula I to prepare polycyclic polymers. The terms "polycycloolefin," "polycycle," and "norbornene-type" monomer are used interchangeably herein to mean an addition polymerizable monomer containing at least one norbornene moiety as shown below:

the simplest polycyclic monomer of the present invention is the bicyclic monomer, bicyclo [2.2.1]hept-2-ene, commonly known as norbornene. The term norbornene-type monomer is meant to include norbornene, substituted norbornene, and any substituted and unsubstituted higher cyclic derivatives thereof, so long as the monomer contains at least one norbornene or substituted norbornene moiety. The substituted norbornenes and higher cyclic derivatives thereof contain pendant hydrocarbyl substituents or heteroatom-containing pendant functional substituents. Typical addition polymerizable monomers are represented by the following formula:

wherein "a" represents a single or double bond, R³¹To R³⁴Independently represents a hydrocarbyl or functional substituent, m is an integer from 0 to 5, and when "a" is a double bond, R is³¹And R³²One and R³³And R³⁴One of which is not present.

When the substituent is a hydrocarbon group, a halogenated hydrocarbon group or a perhalogenated hydrocarbon group, R³¹To R³⁴Independently represents C selected from hydrogen, linear and branched₁-C₁₀Alkyl, straight and branched C₂-C₁₀Alkenyl, straight and branched C₁-C₁₀Alkynyl, C₄-C₁₂Cycloalkyl radical, C₄-C₁₂Cycloalkenyl radical, C₆-C₁₂Aryl, and C₇-C₂₄Aralkyl radicals, halogenated radicals and perhalogenated radicals, R³¹And R³²Or R³³And R³⁴May together represent C₁-C₁₀An alkylene group. Typical alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl. Typical alkenyl groups include, but are not limited to, vinyl, allyl, butenyl, and cyclohexenyl. Typical alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Typical cycloalkyl groups include, but are not limited to, cyclopentyl, cyclohexyl, and cyclooctyl substituents. Typical aryl groups include, but are not limited to, phenyl, naphthyl, and anthracenyl. Typical aralkyl groups include, but are not limited to, benzyl and phenethyl. Typical alkylene groups include methylene and ethylene.

Advantageous perhalogenated hydrocarbon groups include perhalogenated phenyl and alkyl groups. Halogenated compounds suitable for use in the present inventionThe alkyl group being straight-chain or branched and having the formula C_fX”_2f+1Wherein X' is the above-mentioned halogen and f is an integer selected from 1 to 10. Suitable perfluorinated substituents include perfluorophenyl, perfluoromethyl, perfluoroethylPropyl, perfluorobutyl, and perfluorohexyl. In addition to halogen substituents, the cycloalkyl, aryl and aralkyl groups of the present invention may be further substituted with straight and branched C₁-C₅Alkyl and haloalkyl, aryl and cycloalkyl.

When the pendant group is a functional substituent, R³¹To R³⁴Independently represents a group selected from- (CH)₂)_nC(O)OR³⁵、-(CH₂)_n-C(O)OR³⁵、-(CH₂)_n-OR³⁵、-(CH₂)_n-OC(O)R³⁵、-(CH₂)_n-C(O)R³⁵、-(CH₂)_n-OC(O)OR³⁵、-(CH₂)_nSiR³⁵、-(CH₂)_nSi(OR³⁵)₃And- (CH)₂)_nC(O)OR³⁶Wherein n independently represents an integer of O to 10, R³⁵Independently represent hydrogen, straight andbranched C₁-C₁₀Alkyl, straight and branched C₂-C₁₀Alkenyl, straight and branched C₂-C₁₀Alkynyl, C₅-C₁₂Cycloalkyl radical, C₆-C₁₄Aryl, and C₇-C₂₄An aralkyl group. At R³⁵Typical hydrocarbyl groups listed under the definitions of (A) and (B) above for R³¹To R³⁴The same applies under the definition. As previously described in R³¹To R³⁴Listed below at R³⁵The hydrocarbyl groups defined below may be halogenated and perhalogenated. R³⁶Radical represents selected from-C (CH)₃)₃、-Si(CH₃)₃、-CH(R³⁷)OCH₂CH₃、-CH(R³⁷)OC(CH₃)₃Or a part of the following cyclic groups:

wherein R is³⁷Represents hydrogen or linear or branched (C)₁-C₅) An alkyl group. The alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, tert-pentyl and neopentyl. In the above structure, extending from a cyclic groupThe single bond lines indicate the position at which the cyclic group is bonded to the acid substituent. R³⁶Examples of the group include 1-methyl-1-cyclohexyl, isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, 3-oxocyclohexanonyl, mevalonic lactone, 1-ethoxyethyl, and 1-butoxyethyl groups.

R³⁶The radicals may also represent dicyclopropylmethyl (Dcpm) and dimethylcyclopropylmethyl (Dmcp), represented by the following structures:

in the above formula IV, R³¹And R³⁴And the two ring carbon atoms to which they are attached may together represent a substituted or unsubstituted cycloaliphatic radical containing from 4 to 30 ring carbon atoms or a substituted or unsubstituted aryl radical containing from 6 to 18 ring carbon atoms, or a combination thereof. The cycloaliphatic group may be monocyclic or polycyclic. When unsaturated, the cyclic group may contain mono-or polyunsaturated groups, with mono-unsaturated cyclic groups being considered suitable. When substituted, the ring contains one or more substitutions, wherein the substituents are independently selected from hydrogen, straight and branched chain C₁-C₅Alkyl, straight and branched C₁-C₅Haloalkyl, straight and branched C₁-C₅Alkoxy, halogen, or combinations thereof. R³¹And R³⁴The radicals together forming a divalent bridging group-C (O) -G- (O) C-and the two ring carbon atoms to which they are attached together forming a five-membered ring, in which G represents an oxygen atom or N (R)³⁸) Radical, R³⁸Selected from hydrogen, halogen, straight and branched C₁-C₁₀Alkyl, and C₆-C₁₈And (4) an aryl group. The typical structure is represented as follows:

wherein m is an integer of 0 to 5.

Polymerization of monomers

The polycycloolefin monomers of the present invention can be polymerized in solution or in bulk. A catalytic amount of a preformed one-component pro-initiator is added to a reaction medium containing at least one polycyclic olefin monomer. Examples of polycyclic olefin monomers include, but are not limited to, those of formula IV above. The pre-initiator of the present invention is added to a reaction medium containing thedesired monomer or mixture of monomers and polymerized at a suitable pre-initiator activation temperature (i.e., the temperature at which the pre-initiator begins to initiate polymerization of the monomer). If a latent period is desired, the temperature of the reaction medium must be kept below the activation temperature of the pre-initiator used. Typical activation temperatures may range from about ambient room temperature to about 250 ℃. In another embodiment, the activation temperature is in the range of about 40 to about 180 ℃. In yet another embodiment, the activation temperature is in the range of from about 60 to about 130 deg.C, and in yet another embodiment, the activation temperature is 100 deg.C. One of ordinary skill in the art can readily determine the desired activation temperature without undue experimentation based on the pro-initiator compound used, the monomer activity, and the concentration of monomer used in the polymerization reaction relative to the pro-initiator.

Lowering the temperature of the pro-initiator/monomer composition below ambient room temperature may extend the latency and/or storage stability of the composition. This temperature is typically in the range of about-150 c to about just below ambient room temperature (i.e., about 15 c).

In one embodiment of the invention, typical monomer to pro-initiator ratios (i.e., monomer: palladium metal) are used in the range of about 250000: 1 to about 50: 1. In another embodiment, the ratio of monomer to pro-initiator used is in the range of from about 100000: 1 to about 100: 1. In another embodiment, the ratio of monomer to pro-initiator used is in the range of from about 50000: 1 to about 500: 1, and in yet another embodiment the ratio is about 25000: 1.

Pressure is not observed to be important, but may depend on the boiling point of the solvent used, i.e., the pressure sufficient to maintain the solvent in the liquid phase. The reaction is preferably carried out under an inert atmosphere such as nitrogen or argon.

In a typical embodiment of the invention, the weight average molecular weight (Mw) of the resulting polymer is from about 150000 to about 1000000. The molecular weight was measured by Gel Permeation Chromatography (GPC) using polynorbornene standards (modified ASTM D3536-91). The instrument comprises the following steps: alcot708 Autosampler; waters 515 Pump; waters 410 reflective IndexDetector. Column: phenomenex Phenogel line Column (2) and Phenogel106_ Column (all columns are 10 micron packed capillary columns). The sample was transported in monochlorobenzene. Absolute molecular weights of polynorbornene standards were generated using a Chromatics CMX100 low angle laser light scattering instrument.

If desired, α -olefin chain transfer agents may be mixed to control the molecular weight of the polymer, as disclosed in US 6136499, relevant portions of which are incorporated herein by reference, in one embodiment of the invention, α -olefin chain transfer agents are suitable selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, cyclopentene, and cyclohexene.

Solution process

In the solution process, the desired one-component pro-initiator can be added to a solution of the cycloolefin monomer or monomer mixture to be polymerized for the polymerization. In one embodiment, the amount of monomer in the solvent is in the range of about 10 to about 50 weight percent, and in another embodiment in the range of about 20 to about 30 weight percent. After the one-component pre-initiator is added to the monomer solution, the reaction medium is agitated (e.g., stirred) to ensure complete mixing of the pre-initiator and monomer components.

Typical solvents for the polymerization reaction include, but are not limited to, alkane and cycloalkane solvents such as pentane, hexane, heptane, and cyclohexane; halogenated alkane solvents such as dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1-dichloroethane, 1, 2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, and 1-chloropentane; aromatic solvents such as benzene, xylene, toluene, anisole, 1, 3, 5-trimethylbenzene, chlorobenzene, and o-dichlorobenzene, Freon 112 halocarbon solvents, and mixtures thereof.

Body method

The term bulk polymerization means a polymerization reaction that is typically carried out in the substantial absence of a solvent. In some cases, however, a small proportion of solvent may be present in the reaction medium. If it is desired to dissolve the pre-initiator in the solvent before it is added to the monomers, it is possible to introduce a small amount of solvent into the reaction medium. Solvents may also be used in the reaction medium to reduce the viscosity of the polymer at the end of the polymerization reaction to facilitate subsequent use and processing of the polymer. In one embodiment of the invention, the amount of solvent that may be present in the reaction medium is in the range of from about 0 to about 20 weight percent. In another embodiment in the range of from about 0 to about 10 weight percent, and in yet another embodiment in the range of from about 0 to about 1 weight percent of the reaction mixture, based on the weight of monomers present in the reaction mixture. Typical solvents include, but are not limited to, alkane and cycloalkane solvents such as pentane, hexane, heptane, and cyclohexane; halogenated alkane solvents such as dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1-dichloroethane, 1, 2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, and 1-chloropentane; aromatic solvents such as benzene, xylene, toluene, anisole, 1, 3, 5-trimethylbenzene, chlorobenzene, and o-dichlorobenzene; and halocarbon solvents such as Freon 112; and mixtures thereof.

The one-component pro-initiators according to embodiments of the present invention are added to the desired monomer or monomer mixture. The reaction components are mixed and heated to the activation temperature of the initiator before use. Alternatively, the monomer mixture is preheated to the activation temperature of the pre-initiator and the pre-initiator is added to the preheated monomer. The polymerization was then allowed to proceed to completion. After the initial polymerization reaction, the resulting polymer product may be post-cured to remove any residual solvent or unreacted monomer, if desired.

Without wishing to be bound by the inventive theory, it is believed that post-curing is required from the standpoint of maximizing the conversion of monomer to polymer. In the bulk process, the monomer is essentially a diluent for the catalyst system components. As the monomer is converted to polymer, a plateau is reached beyond which the segregation of the components of the catalyst system from the unconverted monomer due to the conversion of the reaction medium to the polymer matrix (vitrification) slows the conversion of monomer to polymer or stops due to loss of fluidity. It is believed that post-curing at elevated temperatures increases the mobility of the reactants within the matrix allowing further conversion of the monomers into polymers.

In embodiments of the invention employing post-curing, the post-cure cycle is carried out at a temperature in the range of about 100 to about 300 ℃ for 1 to 2 hours. In another embodiment in the range of from about 125 to about 200 c, and in yet another embodiment in the range of from about 140 to about 180 c. The curing cycle may be at a constant temperature or may beramped linearly (e.g., incrementally raising the curing temperature from a desired minimum temperature to a desired maximum temperature over a desired curing time period).

In certain embodiments of the invention, it is advantageous to use an excess of the salt of the weakly coordinating anion to carry out the polymerization in a bulk and solution reaction. The appropriate molar ratio of this excess weakly coordinating anion salt to palladium pre-initiator (i.e. [ C]]_e[WCA]_d: pd pre-initiator) is in the range of from 0.1 to 100 molar equivalents in certain embodiments, from 0.5 to 50 molar equivalents in other embodiments, or from 1 to 10 molar equivalents. A favorable WCA salt ([ C]was found]_e[WCA]_d) Including tetrakis (pentafluorophenyl) borate (diethyl ether)_2.5Lithium, dimethylanilinium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, H (OEt)₂)_xTetrakis (pentafluorophenyl) borate, tetrakis [ 4-methyl- α -bis (trifluoromethyl) benzylato-. kappa.O]Aluminates, sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, trialkyl and triaryl tetrakis (pentafluorophenyl) borate, and trityl tetrakis (pentafluorophenyl) borate.

Examples

The following examples are detailed descriptions of methods of preparation and use of certain compositions of the present invention. These preparations are detailed for illustration within the scope of the more generally described methods given above. These examples are for illustration only and are not intended to restrict or otherwise limit the scope of the present invention.

Examples 1 to 10: preparation of Palladium Complex precursors

Example 1

Pd(OAc)₂(P(i-Pr)₃)₂Preparation of

In the presence of N2In a flask of a funnel, P (i-Pr)₃(8.51mL, 44.6mmol) of CH₂Cl₂The solution (20mL) was added dropwise to a red brown Pd (OAc) stirred at-78 deg.C₂(5.00g, 22.3mmol) of CH₂Cl₂(30mL) in suspension. The suspension gradually cleared to a yellow-green solution, allowed to warm to room temperature, stirred for 2 hours, and then filtered through a 0.45 μm filter. The filtrate was concentrated to about 10mL, then hexane (20mL) was added to give a yellow solid, which was filtered off (in air), washed with hexane (5X 5mL), and then dried in vacuo. Yield 10.94g (89%). NMR data:¹H NMR(δ，CD₂Cl₂)：1.37(dd，36H，CHCH₃)，1.77(s，6H，CCH₃)，2.12(m，6H，CH)。³¹P NMR(δ，CD₂Cl₂)：32.9(s)。

example 2

Pd(OAc)₂(P(Cy)₃)₂Preparation of

In a two-necked round-bottomed flask equipped with an addition funnel, red brown Pd (OAc)₂(5.00g, 22.3mmol) of CH₂Cl₂The suspension (50mL) was stirred at-78 ℃. Charging the addition funnel with P (Cy)₃(13.12g, 44.6mmol) of CH₂Cl₂Solution (30mL) was then added dropwise to the stirred suspension over 15 minutes, resulting in a reddish brown color that gradually turned yellow. After stirring at-78 ℃ for 1 hour, the suspension was allowed to warm to room temperature and stirred for an additional 2 hours, then diluted with hexane (20 mL). The yellow solid was then filtered off in air, washed with pentane (5X 10mL) and dried in vacuo. The filtrate was cooled to 0 ℃ and the second batch was isolated by filtration, washing and drying as previously described. Yield 15.42g (88%). NMR data:¹H NMR(δ，CD₂Cl₂)：1.18-1.32(brm，18H，Cy)，1.69(br m，18H，Cy)，1.80(br m，18H，Cy)1.84(s，6H，CH₃)，2.00(br d，12H，Cy)。³¹P NMR(δ，CD₂Cl₂)：21.2(s)。

example 3

trans-Pd(O₂C-t-Bu)₂(P(Cy)₃)₂Preparation of

At 100mL of SchPd (O) in a lenk flask₂C-t-Bu)₂(1.3088g, 4.2404mmol) in CH₂Cl₂(10mL), the flask contents were cooled to-78 ℃ and stirred. To the above solution was slowly added P (Cy) using a syringe₃(2.6749g, 9.5382mmol) of CH₂Cl₂(15mL) the solution was stirred at-78 ℃ for 1 hour and at room temperature for 2 hours. To the above reactionHexane (20mL) was added to the mixture to give the title complex (1.39g) as a yellow solid. The solid was filtered off, washed with hexane (10mL) and then dried under reduced pressure. The solvent was removed from the filtrate to give an orange solid which was then dissolved in CHCl₃The resulting solution was evaporated in a fume hood to give more of the title complex (648mg) in a hexane mixture (1/1: v/v). Total yield 2.04g (2.345mmol), 55%. C₄₆H₈₄O₄P₂Analytical calculation of Pd: c63.54, H9.74%.

Example 4

Pd(OAc)₂(P(Cp)₃)₂Preparation of

Is full of N₂In the flask, red brown Pd (OAc)₂(2.00g, 8.91mmol) of CH₂Cl₂(-25 mL) the suspension was stirred at-78 ℃. Using a sleeve to seal P (Cp)₃(4.25g, 17.83mmol) of CH₂Cl₂The solution (-20 mL) was added dropwise to the stirred suspension over 10 minutes, resulting in a gradual change from orange brown to yellow. The suspension was allowed to warm to room temperature and stirred for an additional 1 hour. The solvent was concentrated (. about.5 mL) and hexane (. about.15 mL) was added to give a yellow solid which was filtered off in air, washed with hexane (5X 10mL) and dried in vacuo. The filtrate was cooled to 0 ℃ and a second batch was isolated by filtration, washing and drying as described in example 3. Yield 4.88g (85%). NMR data:¹H NMR(δ，CD₂Cl₂)：1.52-1.56(br m，12H，Cp₃)，1.67-1.72(br m，12H，Cp₃)，1.74(s，6H，CH₃)，1.85-1.89(br m，12H，Cp₃)，1.96-1.99(br d，6H，Cp₃)，2.03-2.09(br m，12H，Cp₃)。³¹P NMR(δ，CD₂Cl₂)：22.4(s)。

example 5

Pd(O₂CCF₃)₂(P(Cy)₃)₂Preparation of

Pd (O) in a 100mL Schlenk flask₂CCF₃)₂(1.5924g, 4.790mmol) in CH₂Cl₂(10mL), the flask contents were cooled to-78 ℃ and stirred. To the above solution was slowly added P (Cy) using a syringe₃(2.8592g, 10.1954mmol) of CH₂Cl₂(16mL) the flask contents were stirred at-78 deg.C for 1 hour and at room temperature for 2 hours. Hexane (20mL) was added to the reaction mixture to give a yellow solid. The solid was filtered off, washed with hexane (10mL) and dried under reduced pressure to provide the title complex (2.48 g). The solvent was removed from the filtrate to give an orange solid which was then dissolved in THF and the resulting solution was evaporated in a fume hood to give more of the title complex (380 mg). The total yield was 2.86g (3.201mmol), 67%. C₄₀H₆₆O₄P₂F₆Elemental analysis calculated for Pd: c53.78; h7.45 percent. Measurement values: test of1, C53.90, H7.24; run 2, C53.84, H7.08.

Example 6

Pd(O₂CPh)₂(PCy₃)₂Preparation of

Pd (O) in a 100mL Schlenk flask₂CPh)₂(0.742g, 2.126mmol) in CH₂Cl₂(10mL), the flask contents were cooled to-78 ℃ and stirred. To the above solution was slowly added P (Cy) using a syringe₃(1.2814g, 4.569mmol) of CH₂Cl₂(7mL) the flask contents were stirred at-78 deg.C for 1 hour, then at room temperature for 2 hours. The volume of the reaction mixture was reduced to about 7.0mL and diluted with hexane (18mL) to give the title complex as a yellow solid (602 mg). More of the title complex was recovered from the filtrate by the following method. The mother liquor was slowly evaporated in a fume hood during which time the title complex was deposited as a yellow powder (550 mg). The total yield was 60% (1.152g, 1.266 mmol). C₅₀H₇₆O₄P₂Elemental analysis calculated for Pd: c66.03; h8.42 percent.

Example 7

Pd(OAc)₂(P(Cy)₂(CMe₃))₂

Will PCy₂ ^tBu (35.42g, 155mmol) in toluene (50mL) and CH₃CN (100mL) solution was added dropwise to Pd (OAc) cooled to-78 deg.C₂(17.3g, 77.3mmol) of CH₃CN (400mL) suspension. After 10 minutes, the freezing bath was removed and the reddish-brown mixture was allowed to warm to Room Temperature (RT) while stirring. The solution turned orange and a yellow precipitate formed. After stirring for 15 hours, the solvent was removed by rotary evaporation at 25 ℃ to dissolve the resulting oil in Et₂O (130mL), pentane (300mL) was added to precipitate the solid. The solvent was decanted and the solid isolated by filtration. The mother liquor is cooled to-30 ℃ for several hours to isolate a second Pd (OAc)₂(PCy₂t-Bu)₂. The material precipitated as anair stable yellow solid (56.6g, 77.3 mmol).

Example 8

Pd(OAc)₂(P(i-Pr)(CMe₃)₂)₂

Is full of N₂In a flask of (1), red brown Pd (OAc)₂(1.00g, 4.45mmol) of CH₂Cl₂(25mL) the suspension was stirred at-78 ℃ while PtBu was added dropwise over 15 minutes using a cannula₂ ¹Pr (1.68g, 8.90mmol) in CH₂Cl₂(25mL) of the solution (also at-78 deg.C) resulted in a gradual change from reddish brown to orange. The suspension was allowed to warm to room temperature and stirred for 1 hour, during which time the solution was reduced to dryness, leaving a yellow solid. Yield 2.2g (82%).

Example 9

Pd(OAc)₂(P(i-Pr)₂(CMe₃))₂

Is full of N₂In a flask of (1), red brown Pd (OAc)₂(1.00g, 4.45mmol) of CH₂Cl₂(15mL) the suspension was stirred at 0 ℃ while dropping P via cannula over 15 min^tBuⁱPr₂(1.55g, 8.90mmol) of CH₂Cl₂(10mL) of the solution (also at 0 ℃ C.) resulted in a gradual change from reddish brown to orange. The suspension was allowed to warm to room temperature and stirred for 2 hours, during which time the solution was concentrated to about 5mL to give some yellow solid. More solid was obtained by adding petroleum ether (5mL), which was filtered off, washed with hexane (3X 3mL) and dried in vacuo. Yield 1.6g (63%). The filtrate was cooled to-15 ℃ and the precipitate isolated as above to isolate a second batch.

Example 10

Pd(OAc)₂With tricyclopropylphosphine (P (c-Pr)₃) Reaction with LiFeABA

Is full of N₂In a flask of (1), red brown Pd (OAc)₂(0.50g, 2.23mmol) of CH₂C₁₂(15mL) the suspension was stirred at-35 ℃ while PcPr was added dropwise over 5 minutes₃(O.69g, 2.23mmol) of CH₂C₁₂(5mL) of the solution (also at-35 ℃ C.) resulted in a reddish brown color to orange. The suspension was allowed to warm to room temperature and stirred for 1 hour, during which time the filtrate was reduced by about 2-3mL by filtration through a 0.45 μm Teflon filter to give a yellow solid. More solid was obtained by addition of petroleum ether (4mL), which was filtered off, washed with petroleum ether (2X 2mL) and dried in vacuo. Yield 0.80g (68%).

Examples 11 to 19: preparation of palladium pre-initiator compounds without LB adducts

Example 11

[Pd(P(Cy)₃)₂(κ²-O，O′-OAc)][B(C₆F₅)₄]

The method comprises the following steps: PhN (Me)₂HB(C₆F₅)₄(DANFEABA) (1.025g, 1.2793mmol) in dichloromethane (25mL) was added slowly to Pd (OAc)₂(P(Cy)₃)₂(1.004g, 1.2729mmol) in dichloromethane (50mL) was stirred at room temperature for 21 hours. During the above reaction, the color of the reaction mixture turned dark orange. The reaction mixture was devolatilized under reduced pressure to give a paste to which diethyl ether (about 30mL) was added, resulting in the formation of an orange powder. The orange powder was filtered off, washed with acetonitrile and dried in vacuo to give the title compound (1.020 g)0.726mmol) was an air and moisture stable orange solid. The yield was 57%. Diffusion of ether or acetonitrile into a THF solution of the title compound resulted in crystal growth (X-ray structural analysis see figure 2).

The method 2 comprises the following steps: to Pd (P (Cy)₃)₂(OAc)₂Dichloromethane (5mL) was injected into a mixture of (333mg, 424. mu. mol) and 4-toluenesulfonic acid monohydrate (85mg, 446. mu. mol) and stirred for 22 hours. Of reaction mixtures³¹P NMR spectrum showed a new peak at δ P59.0 and no Pd (OAc) was observed₂(P(Cy)₃)₂(δ P ═ 21.3) peak. Thus, Li (Et) was added to the above reaction mixture₂O)_2.5B(C₆F₅)₄(Li(OEt₂)_2.5FABA) (400mg, 459. mu. mol) in dichloromethane (2mL), stirred for 5 minutes and filtered through a medium pore frit. The solvent was removed from the filtrate under reduced pressure to give a foam, which was then triturated with hexane (5mL) and dried under reduced pressure to give a yellow solid (577 mg). The solid was washed with acetonitrile (2X 3mL) to remove unreacted Li (Et)₂O)_2.5B(C₆F₅)₄And dried under reduced pressure to give the title compound (471mg, 335. mu. mol) in 79% yield. C₆₂H₆₉O₂P₂BF₂₀Elemental analysis calculated for Pd: c52.99; h4.95 percent. Measurement values: run 1, C53.30, H5.03; run 2, C53.29, H5.05.

Example 12

[(P(Cy-d₁₁)₃)₂Pd(κ²-O，O-OAc)][B(C₆F₅)₄]Preparation of

Pd (OAc)₂(P(Cy-d₁₁)₃)₂(111mg, 0.130mmol) and p-toluenesulfonic acid (28mg, 0.147mmol) in 2mL CH₂Cl₂Stirring for 12 hours. Addition of Li (Et)₂O)_2.5[B(C₆F₅)₄](133mg, 0.153mmol) of 1mL CH₂Cl₂The solution was stirred for 15 minutes and then filtered. The volatiles were removed in vacuo to give [ (P (Cy-d)₁₁)₃)₂Pd(κ²-O，O-OAc)][B(C₆F₅)₄]As a pale orange powder, 0.166g, 85%.¹P{H}NMR(C₆D₆)：δ36.9ppm。

Example 13

[Pd(κ²-O，O’-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄]Preparation of

To Pd (OAc)₂(P(i-Pr)₃)₂A mixture of (378mg, 694. mu. mol) and 4-toluenesulfonic acid monohydrate (137mg, 720. mu. mol) was poured into dichloromethane (7mL) and stirred for 22 hours. Of reaction mixtures³¹P NMR spectrum showed a new peak at δ P ═ 70.1 and other unidentified products [ δ P ═ 37.1, 54.0(s)]While no Pd (OAc) was observed₂(P(i-Pr)₃)₂(δ P ═ 33.0). Thus, Li (Et) was added to the above reaction mixture₂O)_2.5A solution of FABA (628mg, 720. mu. mol) in dichloromethane (4mL) was stirred for 5 minutes and the solvent was removed under reduced pressure to give an orange solid. The orange solid was then sonicated with diethyl ether (3X 5 mL). During sonication, a yellow powder was precipitated, filtered off and dried under reduced pressure to give the titled compoundCompound (645mg, 0.554mmol), yield 80%. Pd-1165 is a yellow solid. C₄₄H₄₅O₂P₂PdBF₂₀Calculated elemental analysis of (a): c45.36; h3.89 percent. Measurement values: c45.37, H3.88.

Example 14

[Pd(κ²-O，O’-OAc)(P(Cp)₃)₂][B(C₆F₅)₄]

Into a 25mL Schlenk reaction flask, Pd (OAc) was added₂(P(Cp)₃)₂(500mg, 0.71mmol) and 4-toluenesulfonic acid monohydrate (80mg, 0.73mmol) in 10mL CH₂Cl₂. The orange solution was stirred for 22 hours, after which it turned dark purple/brown. Dissolve in 5mL CH dropwise over 5 min with cannula₂C₁₂Li (OEt) of (5)₂)_2.5FABA (640mg, 0.73 mmol). The solution was stirred for 5 minutesAnd then the solvent was removed under vacuum. Redissolving the orange/purple crystals in CH₂Cl₂In (1), filtering with a syringe filter. The filtrate was then turned orange-brown crystals under vacuum. Yield: 0.68g (72%).

Example 15

[Pd(κ²-O，O’-O₂C-t-Bu)(P(Cy)₃)₂][B(C₆F₅)₄]

To Pd (O)₂C-t-Bu)₂(P(Cy)₃)₂A mixture of (448mg, 515mmol) and 4-toluenesulfonic acid monohydrate (107mg, 563mmol) was poured into dichloromethane (18mL) and stirred for 24 h. Of reaction mixtures³¹The P NMR spectrum showed a new peak at δ P ═ 58.6 and no Pd (O) was observed₂C-t-Bu)₂(P(Cy)₃)₂(δ P ═ 17.6) peak. Thus, Li (Et) was added to the above reaction mixture₂O)_2.5A solution of FABA (512mg, 588mmol) in dichloromethane (4mL) was stirred for 10 min and filtered. The filtrate was evaporated to give a gum, triturated with hexane (7mL) and the hexane removed under reduced pressure to give a yellow solid. The solid was dissolved in a small amount of acetonitrile (3X 5mL) and the resulting solution was sonicated for 10 minutes. During sonication, a yellow powder precipitated which was filtered off and dried under reduced pressure to give the title compound (517mg, 0.357mmol) in 69% yield. C₆₅H₇₅O₂P₂PdBF₂Elemental analysis calculated for 0: c53.94; h5.22 percent. Measurement values: run 1, C53.78, H4.98; run 2, C53.85, H4.90.

Example 16

[Pd(κ²-O，O’-O₂CPh)(P(Cy)₃)₂][B(C₆F₅)₄]

The method comprises the following steps: DANFEABA (162mg, 0.203mmol) was added portionwise to the palladium complex of example 6 (0.179g, 0.197mmol) dispersed in diethyl ether (30mL), and stirredFor 72 hours. The volume of the reaction mixture was reduced to 10mL and diluted with hexane (15mL), resulting in the formation of a grey solid. The solid was washed with acetonitrile (3X 6mL) and dried under reduced pressure to giveThe title compound (150mg, 0.1022mmol) was obtained as a yellow solid in 52% yield. C₆₇H₇₁O₂P₂PdBF₂₀Calculated elemental analysis of (a): c, 54.84; h, 4.88 percent. Measurement values: run 1, C54.58, H4.89; run 2, C54.72, H4.71.

The method 2 comprises the following steps: to Pd (O)₂CPh)₂(P(Cy)₃)₂A mixture of (128mg, 0.141mmol) and 4-toluenesulfonic acid monohydrate (0.032mg, 0.170mmol) was poured into dichloromethane (6mL) and stirred for 24 h. Then, Li (Et) was added to the above reaction mixture₂O)_2.5A solution of FABA (154mg, 0.177mmol) in dichloromethane (3mL) was stirred for 10 min and filtered. Removal of volatiles from the filtrate yielded the title compound as a yellow solid (0.192mg), contaminated with traces of unidentified product.

Example 17

[Pd(OAc)(P(c-Pr)₃)]₂(μ-OAc)₂With Li (OEt)₂)_2.5[B(C₆F₅)₄]Reaction of (2)

In a flask filled with N2, yellow [ Pd (OAc)) (P (c-Pr)₃)]₂(μ-OAc)₂(0.25g, 0.47mmol) of CH₂Cl₂(10mL) solution while adding p-toluenesulfonic acid (0.09g, 0.47mmol) in CH₂Cl₂(10mL) of the solution, resulting in a gradual change from yellow to slightly orange. The solution was stirred for 15 minutes during which time Li (OEt) was added₂)_2.5[B(C₆F₅)₄](0.41g, 0.47mmol) of CH₂Cl₂(10mL) of the solution. The resulting yellow/brown suspension was stirred for 15 minutes, then filtered through a 0.45 μm Teflon filter and the yellow filtrate was dried to give a yellow foam. Yield 0.42 g. This substance (0.0004g) was added to CH₂Cl₂(0.1mL) of the solution was added to a pan containing a mixture of decyl norbornene (1.63g) and trimethoxysilyl norbornene (0.37g) and heated to 130 deg.C, the resulting mixture formed a gel in 15 minutes. After 1 hour a solid mass was obtained.

Example 18

[(P(i-Pr₃))₂Pd(κ²-O，O-O₂CCMe₃)][B(C₆F₅)₄]

With 3mL CDCl₃The reaction solution was stirred so that 300mg of cis- [ (P (i-Pr)₃))₂Pd(κ²-P，C-PⁱPr₂CMe₂)(NCMe)][B(C₆F₅)₄]Example 6O (8.7. mu. mol) was dissolved and 1 equivalent of t-BuCO was added₂H (27 mg). The reaction mixture was stirred for 5 minutes, and then volatile components were removed to give [ (P (i-Pr)₃))₂Pd(κ²-O，O-O₂CCMe₃)][B(C₆F₅)₄]Powder product of (yield)95%) by³¹P NMR and¹and H spectrum characterization.³¹P{H}NMR(CDCl₃)：δ31.4ppm。

Examples 19a to 19e

[(P(i-Pr₃)₂Pd(κ²-O，O-OR)][B(C₆F₅)₄]

Series of titles κ²the-O, O' -OAc derivatives 19-a to 19-e were prepared by the following general methods. With 3mL CDCl₃Make 100mg of cis- [ (P (i-Pr)₃)Pd(κ²-P，C-P(i-Pr)₂CMe₂)(NCMe)][B(C₆F₅)₄]Example 60) (8.7. mu. mol) dissolution; 1 equivalent of RCOOH was added. After 5 minutes of reaction, the volatile components are removed to obtain a powdery product³¹P NMR and¹and H spectrum characterization. R is determined below for each of 19a-19e and weight and characterization data for the product is provided.

19a R＝-CF₃

10mg CF₃-COOH (8.8 μmol); 98mg of 19a was obtained in 92% yield.³¹P{H}NMR(CDCl₃)：δ70.8ppm；¹H NMR(CDCl₃)：δ1.51(d，9H，CH₃)；δ1.45(d，9H，CH₃)；δ2.39(m，6H，CH)。

19b R＝-C₆F₅

19mg C₆F₅-COOH (8.9 μmol); 110mg of 19b was obtained with a yield of 96%.³¹P{H}NMR(CDCl₃)：δ75.4ppm；¹H NMR(CDCl₃)：δ1.51(d，9H，CH₃)；δ1.45(d，9H，CH₃)；δ2.38(m，6H，CH)。

19c R＝-p-(CF₃)C₆H₄

17mg p-CF₃-C₆H₄-COOH (8.9 μmol); 101mg of 19c are obtained with a yield of 89%.³¹P{H}NMR(CDCl₃)：δ71.7ppm。¹H NMR(CDCl₃)：δ1.52(d，9H，CH₃)；δ1.47(d，9H，CH₃)；δ2.39(m，6H，CH)。

19d R＝-C₆H₅

11mg C₆H₅-COOH (9.0 μmol); 100mg of 19d was obtained in 93% yield. 3³¹P{H}NMR(CDCl₃)：δ69.8ppm。¹H NMR(CDCl₃)：δ1.51(d，9H，CH₃)；δ1.46(d，9H，CH₃)；δ2.41(m，6H，CH)；δ7.46(t，2H，C₆H₅)；δ7.62(t，1H，C₆H₅)；δ7.92(d，2H，C₆H₅)。

19e R＝-p-(OMe)C₆H₄

13mg p-(OMe)C₆H₄-COOH (8.5 μmol); 103mg of 19e are obtained in 94% yield.³¹P{H}NMR(CDCl₃)：δ68.7ppm。¹H NMR(CDCl₃)：δ1.50(d，9H，CH₃)；δ1.45(d，9H，CH₃)；δ2.38(m，6H，CH)；δ3.86(s，3H，OCH₃)；δ6.91(d，2H，C₆H₄)；δ7.88(d，2H，C₆H₄)。

Examples 20 to 35: preparation of the Pre-initiator Compound with LB adducts

Example 20

trans-[Pd(OAc)(P(Cy)₃)₂(MeCN)][B(C₆F₅)₄]

Mixing Li (Et)₂O)_2.5B(C₆F₅)₄(0.864mg，0.992mmol) acetonitrile (5mL) was slowly added Pd (OAc) also dispersed in acetonitrile (40mL)₂(P(Cy)₃)₂(764mg, 0.972 mmol). The reaction mixture was stirred for 3 hours, filtered through a 0.45 μ filter, and the solvent was removed under reduced pressure to quantitatively obtain the title compound as a solid. The gas phase diffusion of diethyl ether into a toluene or benzene solution of the title compound at room temperature gave crystals suitable for collection of X-ray data. In FIG. 3 trans- [ Pd (OAc)) (P (Cy)₃)₂(MeCN)][B(C₆F₅)₄]Structural diagram of ANORTEP (g). C₆₄H₇₂NO₂P₂BF₂₀Pd.1Et₂Elemental analysis calculated for O: c53.71, H5.44, N0.92%. Measurement values: run 1, C54.13, H5.43, N0.91. Run 2, C53.85, H5.18, N0.93.

Example 21

[(P(Cy-d₁₁)₃)₂Pd(NCMe)OAc][B(C₆F₅)₄]

To 4mL Pd (OAc)₂(P(Cy-d₁₁)₃)₂(76mg, 0.089mmol) of CH₃CN solution, Li (Et) is added dropwise₂O)_2.5[B(C₆F₅)₄](86mg, 0.099mmol) of 0.5mL CH₃CN solution. The reaction mixture was stirred for 3 hours. The precipitated salt was filtered off through a microporous filter. The volatiles were removed in vacuo to give 0.118g (81% yield) of [ (P (Cy-d) as a solid₁₁)₃)₂Pd(NCMe)OAc][B(C₆F₅)₄]。¹P{H}NMR(THF)：δ29.2ppm。

Example 22

[(P(Cy-d₁)₃)₂Pd(NCMe)(OAc)][B(C₆F₅)₄]

To 4mL Pd (OAc)₂(P(Cy-d₁)₃)₂(75mg, 0.095mmol) of CH₃CN solution, Li (Et) is added dropwise₂O)_2.5[B(C₆F₅)₄](84mg, 0.097mmol) of 0.5mL CH₃CN solution. The reaction mixture was stirred for 3 hours. Passing through a microporous filterThe precipitated salt is filtered off. The volatiles were removed in vacuo to yield 0.120g (87.0% yield) of a pale orange solid [ (P (Cy-d)₁)₃)₂Pd(NCMe)(OAc)][B(C₆F₅)₄]。¹P{H}NMR(THF)：δ31.5ppm。

Example 23

[Pd(OAc)(P(i-Pr)₃)₂(MeCN)][B(C₆F₅)₄]

Mixing Li (OEt)₂)_2.5A solution of FABA (0.960g, 1.102mmol) in acetonitrile (10mL) was added slowly to a stirred solution of Pd (OAc)₂(P(i-Pr)₃)₂(0.600g, 1.10mmol) in acetonitrile (20 mL). The resulting yellow/orange solution was stirred for 4 hours during which time a solid formed. The mixture was filtered through a 0.45 μm filter and the filtrate was concentrated to dryness, leaving a yellow solid. Yield 1.224g (93%).¹H NMR(δ，CD₂Cl₂)：1.38(m，36H，-CH₃)，1.92(s，3H，-CCH₃)，2.25(m，6H，-CH)2.42(s，3H，CH₃)。³¹P NMR(δ，CD₂Cl₂)：44.5(s)。

Example 24

trans-[Pd(OAc)(P(i-Pr)₃)₂(NC₅H₅)][B(C₆F₅)₄]

The complex trans- [ Pd (OAc) ((P (i-Pr) is prepared as follows₃)₂(NC₅H₅)][B(C₆F₅)₄]: reacting [ Pd (OAc)) (P (i-Pr)₃)₂(MeCN)][B(C₆F₅)₄](173mg, 0.143mmol) was reacted with pyridine (48mg, 0.60mmol) in dichloromethane (10mL) at ambient temperature for 100 min. Volatiles were removed from the reaction mixture and the resulting residue was triturated with hexane and collected by filtration. The solid was dried under vacuum to give the title complex (177mg, 0.142mmol) in 100% yield.³¹P{1H}NMR(CD₂Cl₂)：δ33.4。¹H NMR(CD₂Cl₂)：δ1.27(m，36H，CH(CH₃)₂)，1.91(s，3H，O₂CCH₃)，1.98(m，6H，CH(CH₃)₂)，7.57(t，³J_HH＝7.2Hz，²H，C₅H₅N)，7.96(t，³J_HH＝7.8Hz，¹H，C₅H₅N)，8.78(d，³J_HH＝4.8Hz，²H，C₅H₅N).¹³C{¹H}NMR(CD₂Cl₂): δ 19.6, 23.5, 24.9 (virtual t,¹J_CP+³J_CP＝9.7Hz，6C，CHMe₂)，124.2(br)，128.0，136.9(d，¹J_cF＝244.9Hz)，138.8(d，¹J_CF＝243.0Hz)，141.3，148.7(d，¹J_CF＝236.8Hz)，154.2，176.7。C₄₉H₅₀NO₂P₂PdBF₂₀.C₅H₅analytical calculation of N: c, 49.01; h, 4.19; and 2.12 percent of N. Measurement values: c, 48.45; h, 3.93; n, 1.81.

Example 25

trans-[(PCy₃)₂Pd(O₂ ¹³C¹³CH₃)(MeCN)][B(C₆F₅)₄]

Prepared by a method analogous to example 20 from trans- [ (PCy)₃)₂Pd(O₂ ¹³C¹³H₃)₂](100mg, 0.127mmol) and [ Li (OEt)₂)_2.5][B(C₆F₅)₄](113mg，0.130mmol)The title complex was prepared in acetonitrile.³¹P{¹H}NMR(CDCl₃)：δ32.3。¹H NMR(CDCl₃)：δ1.17(q，J＝13.2Hz，12H，C₆H₁₁)，1.28(q，J＝13.2Hz，6H，C₆H₁₁)，1.62(q，J＝12.6Hz，12H，C₆H₁₁)，1.77(br d，J＝12.6Hz，6H，C₆H₁₁)，1.91(q，J＝13.2Hz，³⁰H，C₆H₁₁)，2.00(dd，¹J_CH＝128.1Hz，³J_HH＝5.70Hz，³H，O₂ ¹³C¹³CH₃)，2.38(s，³H，CH₃CN)。¹³C{1H}NMR(CDCl₃)：δ3.31，23.4(d，¹Jcc＝54.4Hz，¹C，O₂ ¹³C¹³CH₃) 26.3, 27.9 (virtual t,²J_PC+⁴J_PC5.4Hz), 29.9, 33.7 (virtual t,¹J_PC+³J_PC＝9.4Hz)，124.6(br)，127.2，136.4(d，¹J_CF＝242.2Hz)，138.4(d，¹J_CF＝241.6Hz)，148.4(d，¹J_CF＝242.8Hz)，175.5(d，¹J_CC＝54.4Hz，¹C，O₂ ¹³C¹³CH₃). Using O giving rise to large doublets₂ ¹³C¹³CH₃Of methyl groups¹H NMR signal (600MHz) and with unlabeled O₂CCH₃The much smaller singlet centered at the midpoint of the double doublet of methyl together, obtained by relative integration (some uncertainty in the data, because of some overlap with the resonance of the cyclohexyl group)¹³The C incorporation efficiency was evaluated at 94%.

Example 26

[Pd(OAc)(P(Cp)₃)₂(MeCN)][B(C₆F₅)₄]

In a 50mL Schlenk reaction flask, Li (OEt)₂)_2.5A solution of FABA (0.77g, 0.88mmol) in acetonitrile (20mL) was added slowly via cannula to Pd (OAc) stirred at 0 ℃)₂(P(Cp)₃)₂(0.62g, 0.88mmol) in acetonitrile (20 mL). The resulting yellow solution was allowed to warm to room temperature and stirred for an additional 1 hour, during which time a solid formed. The mixture was filtered through a syringe filter and the filtrate was concentrated to dryness, leaving a yellow foam. Yield: 0.94g (78%).

Example 27

trans-[Pd(O₂C-t-Bu)(P(Cy)₃)₂(MeCN)][B(C₆F₅)₄]

Li (OEt) is stirred₂)_2.5FABA(87.0mg，0.100mmol) of acetonitrile (6mL) was slowly added to Pd (O)₂C-t-Bu)₂(P(Cy)₃)₂(83.6mg, 0.096mmol) of CH₂Cl₂(6mL) in solution. Stirring was continued for 5 hours and the reaction mixture was filtered through a 0.45 μ filter. Volatiles were removed under reduced pressure and the resulting mass was triturated with pentane (10mL) and dried under reduced pressure to give the title compound quantitatively. C₆₇H₇₈NO₂P₂BF₂₀Elemental analysis calculated for Pd: c, 54.06; h, 5.28; n, 0.94 percent.

Example 28

trans-[Pd(O₂CPh)(P(Cy)₃)₂(MeCN)][B(C₆F₅)₄]

Li (OEt) is stirred₂)_2.5A solution of FABA (142mg, 0.164mmol) in acetonitrile (10mL) was slowly added to Pd (O)₂CPh)₂(P(Cy)₃)₂(146mg, 0.161mmol) of CH₂Cl₂(6mL) in solution. Stirring was continued for 15 hours and the reaction mixture was filtered through a 0.45 μ filter. Removal of volatiles under reduced pressure gave the title compound quantitatively. C₆₉H₇₄NO₂P₂PdBF₂₀Calculated elemental analysis of (a): c54.94, H4.94, N0.93%. Measurement values: run 1, C54.75, H4.75, N0.94; run 2, C54.97, H4.62, N0.96.

Example 29

trans-[Pd((O₂C)CF₃)(P(Cy)₃)₂(MeCN)][B(C₆F₅)₄]

Li (OEt) is stirred₂)_2.5A solution of FABA (264mg, 0.303mmol) in acetonitrile (3mL) was slowly added to Pd ((O)₂C)CF₃)₂(P(Cy)₃)₂(266mg, 0.297mmol) in acetonitrile (20 mL). Stirring was continued for 21 hours and the reaction mixture was filtered through a 0.45 μ filter. The solution volume was reduced to 5.0mL to give the title compound as a pale brown powder (263mg, 0.175mmol) in 59% yield. C₆₄H₆₉NO₂P₂PdBF₂₀.CD₃Elemental analysis calculated for CN: c51.28, H4.47, N1.81%. Measurement values: run 1, C51.00, H4.59, N2.12; run 2, C50.99, H4.58, n.2.12.

Example 30

trans-[Pd(OAc)(P(Cy)₃)₂(NC₅H₅)][B(C₆F₅)₄]

Reacting trans- [ Pd (PCy)₃)₂(O₂CMe)(MeCN)][B(C₆F₅)₄](198mg, 0.137mmol) and pyridine (61mg, 0.77mmol) were dissolved separately in toluene (4.0 and 1.OmL, respectively) and cooled to-35 ℃. The toluene solution of pyridine was added to the toluene solution of palladium complex at ambient temperature and stirred at the same temperature for 100 minutes. Volatiles were removed from the reaction mixture under vacuum to give a residue, which was then triturated with hexane (3X 10mL) and collected by filtration. The solid was dried in vacuo to give trans- [ Pd (OAc) (P (Cy))₃)₂(NC₅H₅)][B(C₆F₅)₄](202mg, 0.136mmol), yield 99%.³¹P{¹H}NMR(CDCl₃)：δ22.1。¹H NMR(CDCl₃)：δ1.04(m，12H，C₆H₁₁)，1.22(m，6H，C₆H₁₁)，1.50-1.70(m，18H，C₆H₁₁)，1.71-1.90(m，30H，C₆H₁₁)，2.00(s，3H，O₂CCH₃)，7.54(t，³J_HH＝7.0Hz，2H，C₅H₅N)，7.98(t，³J_HH＝7.8Hz，1H，C₅H₅N)，8.77(d，³J_HH＝4.8Hz，2H，C₅H₅N)。¹³C{¹H}NMR(CDCl₃): δ 23.6, 26.7, 28.2 (virtual t,²J_CP+⁴J_CP＝5.0Hz，C₆H₁₁) 30.2, 34.6 (virtual t,¹J_CP+³J_CP＝8.8Hz，C₆H₁₁)，124.5(br)，127.8，136.8(d，¹J_CF＝253.5Hz)，138.8(d，¹J_CF＝244.3Hz)，140.8，148.7(d，¹J_CF＝237.3Hz)，154.3，176.0。C₆₇H₇₄NO₂P₂PdBF₂₀analytical calculation of (a): c, 54.21; h, 5.02; n, 0.94 percent. Measurement values: c, 54.34; h, 4.92; n, 0.83.

Example 31

trans-[Pd(OAc)(P(Cy)₃)₂(4-Me₂NC₅H₄N)][B(C₆F₅)₄]

From trans- [ Pd (PCy)₃)₂(O₂CMe)(MeCN)][B(C₆F₅)₄](210mg, 0.145mmol) and 4- (dimethylamino) pyridine (20mg, 0.16mmol) were quantitatively prepared in THF (6.0mL) as the title complex trans- [ Pd (OAc) (P (Cy))₃)₂(4-Me₂NC₅H₄N)][B(C₆F₅)₄](221mg)。³¹P{¹H}NMR(CDCl₃)：δ21.8。¹H NMR(CDCl₃)：δ0.95-1.36(m，18H，C₆H₁₁)，1.48-1.95(m，48H，C₆H₁₁)，1.97(s，³H，O₂CCH₃)，3.03(s，6H，N(CH₃)₂)，6.55(d，³J_HH＝6.6Hz，²H，4-Me₂NC₅H₄N)，8.01(d，³J_HH＝6.6Hz，²H，4-Me₂NC₅H₄N)。¹³C{¹H}NMR(CDCl₃): δ 23.7, 26.3, 27.9 (virtual t,²J_CP+⁴J_CP＝5.4Hz，C₆H₁₁) 29.8, 34.0 (virtual t,¹J_CP+³J_CP＝8.8Hz，C₆H₁₁)，39.4，108.8，124.2(br)，136.4(d，¹J_CF＝242.2Hz)，138.3(d，¹J_CF＝243.6Hz)，148.4(d，¹J_CF＝237.9Hz)，151.6，154.7，176.0。C₆₉H₇₉N₂O₂P₂PdBF₂₀analytical calculation of (a): c, 54.25; h, 5.21;n, 1.83 percent. Measurement values: c, 54.17; h, 5.03; n, 1.78.

Example 32

trans-[Pd(OAc)(P(Cy)₃)₂(CNC₆H₃Me₂-2，6)][B(C₆F₅)₄]

From trans- [ Pd (PCy)₃)₂(O₂CMe)(MeCN)][B(C₆F₅)₄](298mg, 0.206mmol) and 2, 6-dimethylphenylene isocyanide (28mg, 0.21mmol) in THF (6.0mL) in quantitative yield the title complex trans- [ Pd (OAc)) (P (Cy)₃)₂(CNC₆H₃Me₂-2，6)][B(C₆F₅)₄](316mg)。³¹P{¹H}NMR(CDCl₃)：δ40.6.¹H NMR(CDCl₃)：δ1.10-1.38(m，18H，C₆H₁₁)，1.60-1.80(m，18H，C₆H₁₁)，1.87(brd，J＝12.0Hz，12H，C₆H₁₁)，2.03(br d，J＝12.0Hz，12H，C₆H₁₁)，2.06(s，3H，O₂CCH₃)，2.16(m，6H，C₆H₁₁)，2.47(s，6H，C₆H₃(CH₃)₂-2，6)，7.24(d，³J_HH＝7.3Hz，²H，C₆H₃(CH₃)₂-2，6)，7.37(t，³J_HH＝7.3Hz，¹H，C₆H₃(CH₃)₂-2，6).¹³C{¹H}NMR(CDCl₃): δ 18.9, 24.4, 26.6, 28.1 (virtual t,²J_CP+⁴J_CP＝5.3Hz，C₆H₁₁) 30.7, 35.6 (virtual t,¹J_CP+³J_CP＝9.4Hz，C₆H₁₁)，124.4(br)，125.7，129.8，132.1，135.4，136.8(d，¹J_CF＝249.9Hz)，138.8(d，¹J_CF＝252.4Hz)，148.7(d，¹J_CF＝243.7Hz)，176.0。C₇₁H₇₈NO₂P₂PdBF₂₀of THFAnalysis calculated value: c, 55.99; h, 5.39; n, 0.87 percent. Measurement values: c, 56.23; h, 5.38; n, 0.78.

Example 33

trans-[(P(i-Pr)₃)₂Pd(O₂CCH₃)(CNC₆H₃Me₂-2，6)][B(C₆F₅)₄]

From 2, 6-dimethylphenylene isocyanide with [ Pd (kappa])²-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄]Or [ Pd (OAc)) (P (i-Pr)₃)₂(MeCN)][B(C₆F₅)₄]Reaction of (2) to prepare trans- [ (P (i-Pr)₃)₂Pd(O₂CCH₃)(CNC₆H₃Me₂-2，6)][B(C₆F₅)₄]。

From [ Pd (kappa])²-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄]

Complexing agent [ Pd (kappa)]²-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄](98mg, 84.1. mu. mol) and 2, 6-dimethylphenylene isocyanide (13mg, 99. mu. mol) were separately dissolved in THF (4.0 and 1.0mL, respectively) and cooled to-35 ℃. Adding a THF solution of 2, 6-dimethylphenylene isocyanide to [ Pd (. kappa.)]²-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄]And stirred at ambient temperature for 2 hours. Removing volatile components from the reaction mixture under vacuum to obtain trans- [ (II) ((III))¹Pr₃P)₂Pd(O₂CCH₃)(CNC₆H₃Me₂-2，6)][B(C₆F₅)₄](108mg，83.4μmol)。

From [ Pd (OAc)) (P (i-Pr)₃)₂(MeCN)][B(C₆F₅)₄]

Complexing agent [ Pd (OAc)) (P (i-Pr)₃)₂(MeCN)][B(C₆F₅)₄](197mg, 0.163mmol) and 2, 6-dimethylphenylene isocyanide (23mg, 0.175mmol) were separately dissolved in dichloromethane (6.0 and 4.0mL, respectively). At ambient temperatureAdding a solution of 2, 6-dimethylphenylene isocyanide in dichloromethane to [ Pd (OAc)) (P (i-Pr)₃)₂(MeCN)][B(C₆F₅)₄]And stirred at the same temperature for 3 hours. Removal of volatiles from the reaction mixture under vacuum quantitatively gave the product as a light brown solidtrans-[(¹Pr₃P)₂Pd(O₂CCH₃)(CNC₆H₃Me₂-2，6)][B(C₆F₅)₄](210mg，0.162mmol)。³¹P{¹H}NMR(CD₂Cl₂)：δ53.8.¹H NMR(CD₂Cl₂)：δ1.42(m，36H，CH(CH₃)₂)，1.96(s，3H，O₂CCH₃)，2.43(s，6H，C₆H₃(CH₃)₂-2，6)，2.47(m，6H，CH(CH₃)₂)，7.22(d，³J_HH＝7.5Hz，²H，C₆H₃(CH₃)₂-2，6)，7.36(t，³J_HH＝7.5Hz，¹H，C₆H₃(CH₃)₂-2，6).¹³C{¹H}NMR(CD₂Cl₂): δ 19.1, 20.1, 24.1, 26.0 (virtual t,¹J_CP+³J_CP＝10.6Hz，CHMe₂)，124(br)，125.5，129.7，132.1，135.7，136.9(d，¹J_CF＝243.0Hz)，138.8(d，¹J_CF＝242.4Hz)，148.7(d，¹J_CF＝239.9Hz)，176.6。C₅₃H₅₄NO₂P₂PdBF₂₀analytical calculation of (a): c, 49.10; h, 4.20; n, 1.08 percent. Measurement values: c, 48.94; h, 3.88; n, 1.52.

Example 34

trans-[Pd(OAc)(P(i-Pr)₂(CMe₃))₂(MeCN)][B(C₆F₅)₄]

Is full of N₂In the flask of (3), red brown Pd (OAc)₂(1.00g, 4.45mmol) of CH₃CN (15mL) suspension was cooled to 0 ℃ and stirredSimultaneously adding P^tBuⁱPr₂(1.55g, 8.90mmol) of CH₃CN (10mL) solution, resulting in a gradual yellowing of the color. The solution was allowed to warm to room temperature and stirred for 30 minutes during which time Li (OEt) was added₂)_2.5[B(C₆F₅)₄](0.41g, 0.47mmol) of CH₃CN (10mL) solution. The resulting yellow/brown suspension was stirred for 1 hour and then filtered through a 0.45 μm Teflon filter and the yellow filtrate was concentrated to dryness to give a yellow foam.

Example 35

[Pd(OAc)(MeCN)(P(Cy₂)t-Bu)₂]B(C₆F₅)₄Preparation of

Adding P (Cy)₂) t-Bu (35.42g, 155mmol) in CH₃CN (100mL) solution was added dropwise to Pd (OAc) which had been cooled to-78 deg.C₂(17.3g, 77.3mmol) of CH₃CN (400mL) suspension. After 10 minutes, the freezing bath was removed and the reddish brown mixture was allowed to warm to Room Temperature (RT) with stirring. The solution turned orange and a yellow precipitate formed. After stirring for 3 hours, Li (Et) was added₂O)_2.5[B(C₆F₅)₄](LiFeABA) (67.3g, 77.3mmol) CH₃CN (150mL) solution. The suspension was stirred for 5 hours, diluted with toluene (100mL), and passed through 1/4 inches of Celite^TMThe filter aid packing is filtered to remove the lithium acetate by-product. The yellow/orange filtrate was concentrated in vacuo to a golden syrup consistency, washed with a 1: 5v/v mixture of diethyl ether and pentane (2X 300)mL), washed with pentane (2X 300mL), and concentrated on a rotary evaporator (35 ℃ C.). Vacuum pumping was performed for 24 hours to obtain [ Pd (OAc) (MeCN) ((Cy)₂)t-Bu)₂]B(C₆F₅)₄(100g, 72mmol, 93%) as an amorphous yellow solid.

Examples 36 to 39: solution polymerization

Example 36

Solution polymerization of decyl norbornene

Stock solutions of these compounds were prepared by dissolving known amounts of the materials shown in Table 1 in dichloromethane (10 mL). From these solutions, 0.1mL of a toluene solution of 5-decylnorbornene (previously purged with nitrogen) was injected, and the resulting solution was heated to 63 ℃ in a sealed bottle. The contents of each vial were heated for 3 hours, then cooled under nitrogen and poured under air into a beaker filled with methanol (125 mL). The resulting methanol-insoluble, colorless polymer was isolated and dried in an oven at 65 ℃ for 20 hours. Unless otherwise stated, all experiments were carried out in toluene (17mL) at 63 ℃ (± 3) for 3 hours, with a concentration of 5-decyl norbornene of 10.7mM and an initiator concentration of 0.4 μ M. The molecular weight was determined using polystyrene standards. 5-decyl norbornene/initiator ratio: 26700.

TABLE 1

Pre-initiator/initiator	Conversion rate (％)	Mw	Mn	Mw/Mn
					[Pd(P(Cy)3)2(k2-O， O′-OAc)][B(C6F5)4]	86	1615000	94300	1.7
[Pd(OAc)(P(Cy)3)2(NCMe)] [B(C6F5)4]	74	1965000	1245000	1.6
					[Pd(OAc)(P(i-Pr)3)2 (MeCN)][B(C6F5)4]	66	1924000	617000	3.1
[Pd(H)(P(Cy3)2(NCCH3)] [B(C6F5)4]	98	1311000	737000	1.8
					[Pd(H)(P(i-Pr)3)2(NCCH3)] [B(C6F5)4]	92	1369000	768000	1.8

The above polymerization details show that the palladium precursor of the present embodiment produces in situ hydrides having substantially the same activity as the Pd-H + initiators of examples 66 and 70.

Example 37

Solution polymerization of decyl norbornene/trimethoxysilyl norbornene with 1-hexene

Decyl norbornene (146.5g) and trimethoxy silane were reacted in a stainless steel reactorDivinylnorbornene (33.5g) and 1-hexene (12.2mL) were mixed with toluene (1170mL) using N₂Purged and stirred at 80 ℃. Adding [ Pd (OAc)) (MeCN) ((P (i-Pr)₃)₂][B(C₆F₅)₄](0.038g) in toluene (10mL) and the solution was stirred for 3 hours. The resulting viscous polymer solution was then precipitated by slow addition of methanol. The resulting white solid polymer was washed with methanol and dried in vacuo. Yield 144.8g (80%) Mn 61868, Mw 152215, PDI 2.46.

Example 38

Solution polymerization of decyl norbornene/trimethoxysilyl norbornene with ethylene

Decyl norbornene (146.5g) and trimethoxysilyl norbornene (33.5g) were mixed with toluene (1170mL) in a stainless steel reactor and N was used₂And (6) purging. Ethylene (300cc) was added and the solution was stirred at 80 ℃. Adding [ Pd (OAc)) (P (i-Pr)₃)₂(MeCN)][B(C₆F₅)₄](0.038g) in toluene (10mL) and the solution was stirred for 3 hours. The resulting viscous polymer solution was then precipitated by slowly adding methanolAnd (4) precipitating. The resulting white solid polymer was washed with methanol and dried in vacuo. Yield 146.7g (82%) Mn-37,815, Mw-100,055, PDI-2.65.

Example 39

Solution polymerization of decyl norbornene with 1-hexene

Decyl norbornene (180.0g) and 1-hexene (12.2mL) were combined with toluene (1170mL) in a stainless steel reactor using N₂Purged and stirred at 80 ℃. Adding [ Pd (OAc)) (P (i-Pr)₃)₂(MeCN)][B(C₆F₅)₄](0.038g) in toluene (10mL) and the solution was stirred for 3 hours. The resulting viscous polymer solution was then precipitated by slow addition of methanol. The resulting white solid polymer was washed with methanol and dried in vacuo. Yield 144.8g (80%) Mn 225,000, Mw 677,000, PDI 3.00.

Example 40

Bulk polymerization of butyl norbornene

Will [ Pd (kappa)]²-O，O′-OAc)P(Cy)₃)₂][B(C₆F₅)₄](0.002g) of CH₂Cl₂(0.1mL) of the solution was added to a pan containing butyl norbornene (5.00g) which had been heated to 130 ℃. Within 10 minutes, the liquid monomer solidified to produce a solid mass.

EXAMPLE 41

Bulk polymerization of butyl norbornene

Reacting [ Pd (OAc)) (P (Cy)₃)₂(MeCN)][B(C₆F₅)₄](0.002g) of CH₂Cl₂(0.1mL) of the solution was added to a pan containing butyl norbornene (5.00g) which had been heated to 130 ℃. Within 10 minutes, the liquid monomer solidified to produce a solid mass.

Example 42

Bulk polymerization of butyl norbornene

Will [ Pd (kappa)]²-O，O′-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄](0.002g) of CH₂Cl₂(0.1mL) of the solution was added to a pan containing butyl norbornene (5.00g) which had been heated to 130 deg.C. Within 10 minutes, the liquid monomer solidified to produce a solid mass.

Example 43

Bulk polymerization of butyl norbornene

Reacting [ Pd (OAc)) (P (i-Pr)₃)₂(MeCN)][B(C₆F₅)₄](0.002g) of CH₂Cl₂(0.1mL) of the solution was added to a pan containing butyl norbornene (5.00g) which had been heated to 130 ℃. Within 10 minutes, the liquid monomer solidified to produce a solid mass.

The polymerizations listed in examples 38-43 all employed a pro-initiator of formula 1, where p ═ r ═ 1. These pro-initiators had a WCA to Pd equivalent ratio of 1: 1. To assess whether the use of excess weakly coordinating anion was beneficial for polymerization, bulk polymerizations of examples 44-47 below were conducted in which additional WCA was provided. In addition, solution polymerization example 48 was also conducted to evaluate the effect of WCA excess on polymer yield.

Examples 44-47 Effect of excess WCA in bulk polymerization

TABLE 2

Example No. 2	Excess equivalent # of DANFEABA	ΔH(J/g)	Peak temperature (. degree. C.)
				44	0	224.6	116.3
45	1	261.4	107.9
				46	2	257.9	109.4
47	4	255.9	83.8

For examples 44-47, an 80: 20 (mol%) mixture of decyl norbornene and trimethoxysilyl norbornene (10g, 43mmol) was loaded with the pre-initiator [ Pd (OAc)) (P (i-Pr)₃)₂(NCMe)][B(C₆F₅)₄](2.1mg, 1.74. mu. mol) and an equivalent excess of WCA salt-shown in Table 2PhN(Me)₂HB(C₆F₅)₄(DANFEABA) (relative to the proinitiator)Equivalent of Pd). The reaction mixture was then heated from room temperature to 300 ℃ at a rate of 10 ℃/min, and Δ H and peak temperature were measured using a Differential Scanning Calorimeter (DSC). In all cases, the resulting thermoset was substantially fully cured.

As a result: as shown in Table 1, the addition of excess WCA salt resulted in a reduction in the peak temperature of the polymerization (reduction in the activation temperature of the polymerization) compared to the control of example 44. Thus, a formulation containing excess WCA salt can fully cure at a lower temperature than a similar formulation without the excess WCA salt.

Example 48

Effect of excess WCA salt in solution polymerization

Decyl norbornene (146.5g), trimethoxysilyl norbornene (33.5g), PhN (Me)₂HB(C₆F₅)₄(DANFEABA; 0.075g) and 1-hexene (12.2mL) were mixed with toluene (1170mL) and treated with N₂Purged and stirred at 80 ℃. Adding [ Pd (OAc) (MeCN) (P)ⁱPr)₃)₂]B(C₆F₅)₄(0.038g) in toluene (10mL) and the solution was stirred for 3 hours. The resulting viscous polymer solution was then precipitated by slow addition of methanol. The resulting white solid polymer was washed with methanol and dried in vacuo. Yield 174.8g (97%). As a result: an almost 20% increase in yield is observed compared to the polymerization carried out without WCA (example 37).

Examples 49 to 50 (comparative examples)

In situ polymerization of decyl norbornene/trimethoxysilyl norbornene two-component initiator systems

In a vial, a mixture of decyl norbornene (8.6g) and trimethoxysilyl norbornene (1.9g) was loaded with Pd (OAc)₂(P(i-Pr)₃)₂(0.001g) and Li (OEt)₂)_2.5FABA (0.006g) was stirred at room temperature (about 20 ℃ C.). The solution gelled within 30 minutes.

Example 50 (comparative example)

In a small bottleEndo, to a mixture of decyl norbornene (8.6g) and trimethoxysilyl norbornene (1.9g), Pd (OAc)₂(P(i-Pr)₃)₂(0.001g) and DANBABA (0.006g) were stirred at room temperature (about 20 ℃). The solution gelled within 30 minutes.

Example 51

One-component pre-initiator

In a vial, a mixture of decyl norbornene (8.6g) and trimethoxysilyl norbornene (1.9g) was loaded with [ Pd (OAc) (MeCN)) (P (i-Pr)₃)₂][B(C₆F₅)₄](0.002g) of CH₂Cl₂(0.1mL) the solution was stirred at room temperature (about 20 ℃). The solution showed only a small increase in viscosity over 48 hours.

Example 52 (comparative example)

Pd(OAc)₂(P(Ph)₃)₂Reaction with trityl FABA

Pd (OAc)₂(P(Ph)₃)₂(25mg, 33.4. mu. mol) of CD₂Cl₂(0.5mL) solution was stirred while trityl FABA (31mg, 33.4. mu. mol) CD was added dropwise through a pipette₂Cl₂(0.5mL) solution. The resulting dark red/black solution was sealed in an NMR tube and analyzed by NMR. As a result:¹h and³¹p NMR analysis indicated the formation of at least 6 products including ortho-metalated products.

Example 53 (comparative example)

Pd(OAc)₂(P(Ph)₃)₂With Li (OEt)₂)_2.5Reaction of FABA

Pd (OAc)₂(P(Ph)₃)₂(25mg, 33.4. mu. mol) of CD₂Cl₂(0.5mL) solution was stirred while Li (OEt) was added dropwise through a pipette₂)_2.5CD of FABA (29mg, 33.4. mu. mol)₂Cl₂(0.5mL) solution. The resulting dark red solution was sealed in an NMR tube and analyzed by NMR.As a result:¹h and³¹p NMR analysis indicated the formation of at least 6 products including ortho-metalated products.

Example 54 (comparative example)

Pd(OAc)₂(P(Ph)₃)₂Reaction with DANFEABA

Pd (OAc)₂(P(Ph)₃)₂(25mg, 33.4. mu. mol) of CD₂Cl₂(0.5mL) solution was stirred while CD of DANFEABA (27mg, 33.4. mu. mol) was added dropwise through a pipette₂Cl₂(0.5mL) solution. The resulting dark red solution was sealed in an NMR tube and analyzed by NMR. As a result:¹h and³¹p NMR analysis indicated the formation of at least 6 products including ortho-metalated products.

Example 55 (comparative example)

Pd(OAc)₂(P(Ph)₃)₂With Li (OEt)₂)_2.5FABA in CD₃Reaction in CN to obtain [ Pd (OAc)) (P (Ph)₃)₂(CD₃CN)][FABA]

Pd (OAc)₂(P(Ph)₃)₂(25mg, 33.4. mu. mol) of CD₃CN (0.5mL) solution was stirred while Li (OEt) was added dropwise through a pipette₂)_2.5CD of FABA (29mg, 33.4. mu. mol)₃CN (0.5 mL). The resulting yellow solution was sealed in an NMR tube and analyzed by NMR. As a result:¹h and³¹p NMR analysis all indicated the formation of a single product.³¹P{¹H}NMR(CD₃CN，δ)：32.8(s)。

From comparative examples 49 to 51 Pd (OAc) can be inferred₂(P(Ph)₃)₂Reaction with various salts of weakly coordinating anions does not produce separable pro-initiator products. The selection or addition of Lewis base, i.e. acetonitrile, to the reaction results in the formation of stable trans- [ Pd (P (Ph))₃)₂(OAc)(MeCN)]Triarylphosphine complexes of the FABA type.

Example 56 (comparative example)

Pd (OAc) at room temperature₂(P(i-Pr)₃)₂Reaction with trityl FABA

Light yellow Pd (OAc)₂(P(i-Pr)₃)₂(40mg) was metered into an NMR tube. By injectionThe syringe is added into the tube dropwise to dissolve 0.75mL of CD₂Cl₂68mg (1eq) of trityl FABA. The yellow solution immediately turned dark gold brown. The solution was mixed thoroughly and then subjected to NMR test. As a result: confirmation of Presence [ Pd (kappa.)]²-O，O′-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄]Is a very trace of product: (³¹One of 12 signals in P NMR).

Example 57 (comparative example)

Pd (OAc) at room temperature₂(P(Cy)₃)₂Reaction with trityl FABA to give [ Pd (kappa])²-O，O′-OAc)(P(Cy)₃)₂][FABA]

Light yellow Pd (OAc) was measured in an NMR tube₂(P(Cy)₃)₂(40 mg). The solution in 0.75mL CD was added dropwise to the tube using a syringe₂Cl₂47mg (1eq) of trityl FABA. The yellow solution immediately turned black. The solution was mixed thoroughly and then subjected to NMR test. As a result:³¹p NMR confirmation [ Pd (κ)²-O，O′-OAc)₂(P(Cy)₃)₂]FABA is the only product.³¹P{¹H}NMR(CD₃CN，δ)：58.9(s)。

Example 58 (comparative example)

Pd (OAc) at room temperature₂(P(i-Pr)₃)₂Reaction with trityl FABA in acetonitrile to obtain [ Pd (OAc)) (P (i-Pr)₃)₂(NCCH₃)][FABA]

30mg of pale yellow Pd (OAc) are metered into the NMR tube₂(P(i-Pr)₃)₂. The solution was added dropwise to the tube using a syringe and dissolved in 0.75mL of MeCN-d₃51mg (1eq) of trityl FABA.The solution immediately turned dark brown, then yellow and precipitated with a light color. Adding four drops of toluene-d₈The precipitate was dissolved. The solution was mixed thoroughly and then subjected to NMR test. As a result:¹h and³¹p NMR analysis all showed a single product.³¹P{¹H}NMR(CD₃CN，δ)：44.8(s)。

Example 59 (comparative example)

Pd (OAc) at room temperature₂(P(Cy)₃)₂Reaction with trityl FABA in acetonitrile to give [ Pd (OAc)) (P (Cy)₃)₂(NCMe-d₃)]FABA

30mg of pale yellow Pd (OAc) are metered into the NMR tube₂(P(Cy)₃)₂. The solution was added dropwise to the tube using a syringe and dissolved in 0.75mL of MeCN-d₃35mg (1eq) of trityl FABA. The solution immediately turned dark brown and then yellow. The solution was mixed thoroughly and then subjected to NMR test. As a result:³¹p NMR confirmed the formation of a single product [ Pd (OAc)) (P (Cy)₃)₂(NCMe-d₃)][FABA]。³¹P{¹H}NMR(CD₃CN，δ)：32.7(s)。

From comparative examples 58 to 59 it can be concluded that: stable complexes can be obtained with trityl FABA and the appropriate trialkylphosphine in the absence of Lewis bases. Trityl FABA in combination with Lewis bases is also an advantageous method for preparing trialkylphosphine containing complexes.

Example 60

cis-[Pd(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(P(i-Pr)₃)(d₃-MeCN)][B(C₆F₅)₄]Preparation of

To [ Pd (kappa)]²-O，O′-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄](0.1625g, 0.1395mmol) of acetonitrile-d₃Sodium carbonate (0.1914g, 1.8058mmol) was added to the solution (3.5mL) and the resulting heterogeneous mixture was stirred at room temperature for 15 hours. The reaction mixture was filtered, and the volatile matter was removed from the filtrate under reduced pressure to give cis- [ Pd (. kappa.) -²-P，C-P(i-Pr)(C(CH₃)₂)(P(i-Pr)₃)(d₃-MeCN)][B(C₆F₅)₄]The wax of (0.1546 g).³¹P{¹H}NMR(CD₃CN): δ 51.7(d, unmetallized phosphorus), 43.2(d, metallized phosphorus),²Jpp＝30.23Hz。³¹P{¹H}NMR(THF-d₈): δ 52.4(br, unmetallized phosphorous), 44.0(br, metalized phosphorous).¹H NMR(THF-d₈)：δ1.29(m，18H，CH(CH₃)₂)，1.46(dd，J＝17.4Hz；15.3Hz，12H，CH(CH₃)₂and d，J＝17.4Hz，6H，C(CH₃)₂)，1.63(dd，J＝12.75Hz；9.75Hz，6H，CH(CH₃)₂)，2.21(m，3H，CH(CH₃)₂)，2.65(m，²H，CH(CH₃)₂).¹³C{¹H}NMR(THF-d8)：δ1.33(m)，20.1，20.4(d，J＝5.1Hz)，20.5(m)，21.9，23.8(br)，45.7(br)，125.4(br)，137.1(d，¹J_CF＝242.40Hz)，139.1(d，¹J_CF＝243.00Hz)，149.2(d，¹J_CF240.60 Hz). No CD observed₃Peak of CN.

In a similar manner, cis- [ Pd (. kappa.) can be prepared in proteo-acetonitrile²-P，C-P(i-Pr)₂(C(CH₂)CH₃)(P(i-Pr)₃)(MeCN)][B(C₆F₅)₄]。

Example 61

cis-[Pd(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(P(i-Pr)₃)(NC₅H₅)][B(C₆F₅)₄]Preparation of

General formula [ Pd (kappa)]²-O，O′-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄]The compound (0.5079g, 0.4360mmol) was dissolved in dichloromethane (6.0mL) and stirred. To the above solution was added pyridine (0.164g, 2.073mmol) in dichloromethane (6mL) under air and stirred for 5 hours. The initially light orange color slowly disappeared to form a colorless solution. The volatile matter was removed under reduced pressure to give the title compound (490mg) in 95% yield. Pentane (or heptane) vapor was diffused to cis- [ Pd (κ) over a period of 3 days in an NMR tube (5mm, 9inch)²-P，C-P(i-Pr)₂(C(CH₃)₂)(P(i-Pr)₃)(NC₅H₅)][B(C₆F₅)₄]Resulting in crystal growth in ether solution (X-ray structure see fig. 4). Unambiguous by two-dimensional HMQC, HMBC, and COSYNMR spectroscopic measurementsGround determination¹H and¹³and (4) C peak.³¹P{¹H}NMR(CDCl₃)：δ49.1(d)，37.2(d)；²J_pp＝29.28Hz.¹H NMR(CDCl₃)：δ1.14-1.21(m，24H，CH(CH₃)₂，ring-C(CH₃)₂)，1.41-1.47(m，12H，ring-CH(CH₃)₂)，2.00(m，3H，CH(CH₃)₂)，2.52(m，2H，ring-CH(CH₃)₂)，7.50(t，³J_HH＝6.30Hz，2H，C₅H₅N)，7.87(t，³J_HH＝7.20Hz，¹H，C₅H₅N)，8.51(d，³J_HH＝4.20Hz，²H，C₅H₅N).¹³C{¹H}NMR(CDCl₃)：δ20.1，20.3，21.8，22.5，24.6(d，¹J_CP＝13.8Hz)，24.8(d，¹J_CP＝26.77Hz)，40.9(dd，²J_PC＝45.98，28.27Hz，¹C，ring-C(CH₃)₂)，124.1(br)，126.2，136.4(d，¹J_CF＝245.40Hz)，138.4(d，¹J_CF＝244.20Hz)，138.8，148.4(d，¹J_CF＝237.30Hz)，151.1。C₄₇H₄₆NP₂PdBF₂₀Analytical calculation of (a): c, 47.68; h, 3.92; n, 1.18 percent. Measurement values: c, 47.67; h, 3.63; and N, 1.17. See the block diagram of fig. 4.

Example 62

cis-[Pd(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(P(i-Pr)₃)(2，6-Me₂py)][B(C₆F₅)₄]Preparation of

In a small bottle [ Pd (P (i-Pr))₃)₂(κ²-O，O′-OAc)][B(C₆F₅)₄](0.102g) was dissolved in methylene chloride (1.0mL), to which was added 2, 6-lutidine (0.0095 g). The solution was stirred at room temperature for 1 hour, then the solution was filtered and the solvent was evaporated to give the product.³¹P{¹H}NMR(CD₂Cl₂)：δ46.71(d)，33.53(d)；²Jpp＝31.30Hz。

Example 63

cis-[Pd(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)P(i-Pr)₃)(2，6-Me₂pyz)][B(C₆F₅)₄]Preparation of

In a small bottle [ Pd (P (i-Pr))₃)₂(κ²-O，O′-OAc)][B(C₆F₅)₄](0.102g) was dissolved in methylene chloride (1.0mL), to which was added 2, 6-lutidine (0.0095 g). The solution was stirred at room temperature for 1 hour, then the solution was filtered and the solvent was evaporated to give the product.³¹P{¹H}NMR(CD₂Cl₂)：δ47.18(d)，35.92(d)；²J_PP＝31.65Hz。

Example 64

cis-[Pd(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)P(i-Pr)₃)(4-t-BuC₅H₄N)][B(C₆F₅)₄]Preparation of

Prepared by a procedure similar to that employed for the preparation of the compound of example 61 from [ Pd (P (i-Pr)]₃)₂(κ²-O，O′-OAc)][(B(C₆F₅)₄](0.5034g, 0.4321mmol) and 4-tert-butylpyridine (0.2282g, 1.6877mmol) in dichloromethane (10mL) prepared the title compound in 95% yield. 31P¹H}NMR(CDCl₃)：δ49.2(d)，36.4(d)；²Jpp＝32.94Hz.1H NMR(CDCl₃)：δ1.11-1.25(m，²⁴H，CH(CH₃)₂，ring-C(CH₃)₂)，1.33(s，9H，C(CH₃)₃)，1.40(dd，³J_HH＝7.10Hz；³J_PH＝4.95Hz，6H，ring-CH(CH₃)₂)，1.46(dd，³J_HH＝7.20Hz，³J_PH＝5.10Hz，6H，ring-CH(CH₃)₂)，1.99(m，3H，CH(CH₃)₂)，2.50(m，²H，ring-CH(CH₃)₂)，7.48(d，³J_HH＝6.00Hz，²H，4-Bu^tC5H4N)，8.36(d，³J_HH＝6.00Hz，²H，4-t-BuC₅H₄N).¹³C{¹H}NMR(CDCl₃)：δ20.2，20.4(d，²J_PC＝3.15Hz)，21.9(d，²J_PC＝2.55Hz)，22.6(m)，24.6(d，¹J_CP＝13.95Hz)，24.7(dd，¹J_CP＝25.20Hz；³J_CP＝3.15Hz)，30.3，35.4，40.5(dd，²J_PC＝46.20；29.30Hz，1C，ring-C(CH₃)₂)，123.3，124.0(br)，136.4(d，¹J_CF＝245.40Hz)，138.4(d，¹J_CF＝244.80Hz)，148.4(d，¹J_CF＝240.30Hz)，150.6，164.1。C₅₁H₅₄NP₂PdBF₂₀Analytical calculation of (a): c, 49.39; h, 4.39; and N, 1.13%. Measurement values: c, 49.54; h, 4.15; n, 1.44.

Example 65

Polymerization of decyl norbornene and trimethoxysilyl norbornene with a metallized triisopropylpalladium phosphine photoinitiator

Influence of Lewis bases in Pd metalates in bulk polymerization

TABLE 2

Example No. 2	Lewis Base (LB)	ΔH(J/g)	Peak temperature (. degree. C.)
				60	MeCN	232.5	114.3
61	NC5H5	261.4	142.4
				62	2，6-Me2py	249.5	141.7
63	2，6-Me2pyz	232.3	132.2

For examples 60-63, an 80: 20 (mol%) mixture (10g) of decyl norbornene and trimethoxysilyl norbornene was loaded with the pro-initiator cis- [ Pd (. kappa.). kappa.1 in a molar ratio of 25000: 1²-P，C-P(i-Pr)₂(C(CH₂)CH₃)(P(i-Pr)₃)(LB)][B(C₆F₅)₄]. The reaction mixture was then heated from room temperature to 300 ℃ at a rate of 10 ℃/min, and Δ H and peak temperature were measuredusing a Differential Scanning Calorimeter (DSC). In all cases, the resulting thermoset was substantially fully cured. Bulk polymerization (30 min at 80 ℃ C./30 min at 130 ℃ C.) was carried out and DSC was tested to determine residual monomer. As a result: as shown in Table 2, the Lewis base concentration increased the peak temperature of polymerization (higher activation temperature of polymerization) as compared with the control of example 60. Thus, the addition of a suitable Lewis base may improve the presence of cis- [ Pd (. kappa.) in the composition²-P，C-P(i-Pr)₂(C(CH₂)CH₃)(P(i-Pr)₃)(LB)][B(C₆F₅)₄]Latency (extended shelf life or pot life) of a formulation of a substance.

Examples 66 to 67

Preparation of hydride and deuterium derivatives of cationic palladium hydride initiators

Example 66

trans-[(Cy₃P)₂Pd(H)(MeCN)][B(C₆F₅)₄]Preparation of

Feeding Pd (H) Cl (PCy) maintained at 0 ℃ through a cannula₃)₂(300mg, 0.43mmol) in acetonitrile (30.0mL) was added [ Ag (toluene)₃][B(C₆F₅)₄](415mg, 0.43mmol) in acetonitrile (20 mL). The resulting mixture was stirred for 1 hour, and then filtered to remove the precipitated AgCl. Volatiles were removed under vacuum to give a yellow foam. Yield 520mg (88%).¹HNMR(CDCl₃)：δ-15.34(t，²JPH＝6.9Hz，¹H，PdH)，1.10-1.53(m，33H，C₆H₁₁)，1.70-2.05(m，33H，C₆H₁₁)，2.28(s，3H，CH₃CN).³¹P{¹H}NMR(CDCl₃)：δ43.6。C₆₂H₇₀NP₂PdBF₂₀Analytical calculation of (a): c, 53.64; h, 5.08; andN, 1.01 percent. Measurement values: c, 53.64; h, 5.07; n, 0.96. Or, by [ Me₂(H)NC₆H₅][B(C₆F₅)₄]And [ Pd (PCy)₃)₂]The title compound was prepared in quantitative yield by reaction in acetonitrile at room temperature.

Example 67

trans-[(Cy₃P)₂Pd(²H)(MeCN)][B(C₆F₅)₄]Preparation of

HN (CH)₃)₂Ph[B(C₆F₅)₄(2.50g, 3.1mmol) in 1: 1 toluene and CH₂Cl₂The green suspension in the mixture (50mL) was stirred and strictly degassed D was added₂O (2 mL). The suspension almost immediately cleared to a two-phase mixture of a clear aqueous layer and a soluble greenish organic layer. The mixture was stirred for 2 hours, the organic layer was decanted off through a cannula and concentrated to dryness, leaving a very pale green solid. Yield 2.32 g.¹H NMR showed only 15% remaining N-H, and²HNMR clearly showed incorporation of N-H bonds²H。

Pd (PCy)₃)₂(0.50g, 7.5mmol) and²HN(CH₃)₂Ph[B(C₆F₅)₄](0.60g, 7.5mmol) in d₃The suspension in MeCN (5mL) was stirred for 2 hours, during which an aliquot was removed for analysis.¹H and³¹p NMR shows the formation of [ Pd: (A)²H)(MeCN)(PCy₃)₂][B(C₆F₅)₄]Without any remaining material, the aliquot was returned to the parent suspension and the remaining solids were filtered off. The filtrate was concentrated to dryness, leaving a beige foam. Yield 0.73 g.¹H、²H and³¹PNMR showed the desired product had formed with about 50% incorporation of Pd-H bonds²H. It has also beenobserved that in PCy₃Incorporating some into the radical²H。

Examples 68 and 69

(Effect of isotopic labeling on latency)

Example 68

By PCy₃And d₃₃-PCy₃Polymerization of decyl norbornene and trimethoxysilyl norbornene with palladium-based proinitiators

Two vials were charged with an 80: 20 (mol%) mixture of decyl norbornene and trimethoxysilyl norbornene (2g, 8.7mmol) and a magnetic stir bar, respectively. To one of the bottles (bottle 68a) was added [ Pd (OAc) (MeCN) (PCy)₃)₂][B(C₆F₅)₄](Pd 1446；0.5mg，3.5×10^-7mol) of CH₂Cl₂The solution (100. mu.L) was added to another bottle (68 b) [ Pd (OAc) (MeCN) (d)₃₃-PCy₃)₂][B(C₆F₅)₄](d66-Pd 1446；0.5mg，3.5×10^-7mol) of CH₂Cl₂Solution (100. mu.L). Both bottles were sealed and stirred at ambient temperature (21 ℃). After 48 hours, the solution in bottle 68a was significantly more viscous than the solution in bottle 68 b. After 100 hours, the solution in bottle 68a was almost unable to flow, while the solution in bottle 68b flowed much more easily. Both samples were placed in an oven at 130 ℃ for 1 hour. Both samples cured to a solid.

Example 69

Polymerization of decyl norbornene and trimethoxysilyl norbornene with Pd-H and Pd-D based Palladium Pre-initiators

Two vials were charged with an 80: 20 (mol%) mixture of decyl norbornene and trimethoxysilyl norbornene (2g, 8.7mmol) and a magnetic stir bar, respectively. To one of the bottles (bottle 69a) was added [ Pd (H) (MeCN) (PCy)₃)₂][B(C₆F₅)₄](Pd 1388；0.5mg，3.5×10^-7mol) of CH₂Cl₂The solution (100. mu.L) was added to the other bottle (bottle 69b) with [ Pd: (II) ((III))²H)(MeCN)(PCy₃)₂][B(C₆F₅)₄](d₁-Pd 1388；0.5mg，3.5×10^-7mol) ofCH₂Cl₂Solution (100. mu.L). Both bottles were sealed and stirred at ambient temperature (21 ℃). After 24 hours, the solution in vial 69a was significantly more viscous than the solution in vial 69 b. Both samples were placed in an oven at 130 ℃ for 1 hour. Both samples cured to a solid.

Example 70

trans-[(P-i-Pr₃)₂Pd(H)(MeCN)][B(C₆F₅)₄]Preparation of

Trans- [ (P-i-Pr)₃)₂Pd(H)Cl](292mg, 0.630mmol) was stirred in acetonitrile (6.0mL) and cooled to-35 ℃. To this suspension was slowly added cold (-35 deg.C) Ag (toluene)₃][B(C₆F₅)₄](683mg, 0.642mmol) in dichloromethane (6.0 mL). The resulting reaction mixture yielded a precipitate (presumably AgCl) over 15 minutes and was stirred at room temperature for 2 hours. The solution was then filtered through a 0.45 μm filter and the volatiles were removed under vacuum to removeA quantitative yield (99%) gave 723mg trans- [ (P-i-Pr)₃)₂Pd(H)(MeCN)][B(C₆F₅)₄]。C₄₄H₄₆NP₂PdBF₂₀Analytical calculation of (a): c, 46.04; h, 4.04; n, 1.22%. Measurement values: c, 45.88; h, 3.71; and N, 1.02.³¹P{1H}NMR(CDCl₃)：δ55.5.¹H NMR(CDCl₃)：δ-15.26(t，²JPH＝7.35Hz，1H，PdH)，1.23(m，36H，CH(CH₃)₂)，2.14-2.26(m，6H，CHMe₂)，2.28(s，3H，CH₃CN).¹³C{¹H}NMR(CDCl₃): δ 2.5, 20.2, 24.9 (virtual t,¹J_CP+³J_CP＝11.0Hz)，124.0(br)，125.3，136.4(d，¹J_CF＝238.3Hz)，138.4(d，¹J_CF＝239.7Hz)，148.4(d，¹J_CF＝236.5Hz)。

examples 71 to 74

Preparation and reactivity of arsine derivatives

Example 71

Pd(As-i-Pr₃)₂(O₂CCH₃)₂

By Dyke, w.j.c.; method for preparing triisopropylarsine (As-i-Pr) by Jones, W.J (J.chem.Soc.1930, 2426-one 2430)₃)。AsCl₃(21.6mmol) was reacted with i-PrMgCl (76mmol) in diethyl ether and vacuum distilled (b.p.37 ℃/3mmHg), 2.90g, 65.7% yield.¹H NMR(CDCl₃)：δ1.18ppm(d，18H，CH₃，JHH＝7.2Hz)；δ1.86(m，3H，CH)。

Under nitrogen atmosphere to stirred Pd (OAc)₂(0.229g, 1.20mmol) in chloroform (10mL) was added As-i-Pr₃(0.420g, 2.06mmol) and stirred for 1 hour. The solvent was removed in vacuo and the residue was washed with hexane to give 0.630g (97.5%) of a pale yellow powder.¹H NMR(400MHz，CDCl₃)：δ1.41ppm(d，36H，CH₃)；δ2.26(m，6H，CH)；δ1.79(s，6H，CH₃COO)。

Example 72

[Pd(As-i-Pr₃)₂(κ²-O₂CCH₃)₂)][(B(C₆F₅)₄]

Pd (As-i-Pr) with 10mL of dichloromethane₃)₂(O₂CCH₃)₂(0.321g, 0.507mmol) and p-toluenesulfonic acid (HOTs) (0.102g, 0.536mmol) were dissolved. The mixture was stirred at room temperature under nitrogen for 22 hours. 5mL of Li (Et) was added₂O)_2.5[B(C₆F₅)₄](0.470g, 0.539mmol) in dichloromethane, and stirred at room temperature for 15 minutes. The precipitated salt is filtered offLiOAc and volatiles were removed in vacuo. The viscous residue was washed with hexane and diethyl ether; after filtration and vacuum drying, 0.175g (yield 28%) of a bright yellow powdery product was collected.¹HNMR(400MHz，CDCl₃)：δ1.47ppm(d，36H，CH₃)；δ2.50(m，6H，CH)；δ2.03(s，3H，CH₃COO)，CH)。

Example 73

[Pd(As-i-Pr₃)₂(O₂CCH₃)(NCCH₃)][(B(C₆F₅)₄]

Make Pd (OAc)₂(As-i-Pr₃)₂(0.191g, 0.302mmol) and Li (Et)₂O)_2.5[B(C₆F₅)₄](0.263g, 0.302mmol) in CH₃CN (10 mL). The reaction mixture was stirred at room temperature under nitrogen for 4 hours, then the solvent was removed in vacuo to give the product as a very viscous brown oil. The residue was washed with 2X 3mL hexane and then dried in vacuo to give a yellow dry powder, 0.354g (91%).¹H NMR(400MHz，CDCl₃)：δ1.43ppm(d，36H，CH₃)；δ2.45(m，6H，CH)；δ1.92(s，3H，CH₃COO)，δ2.35(s，3H，CH₃CN)。

Example 74

Polymerization of decyl norbornene/trimethoxysilyl norbornene

Reacting [ Pd (As-i-Pr)₃)₂(O₂CCH₃)(NCCH₃)][B(C₆F₅)₄](0.0005g) CH₂Cl₂(0.1mL) of the solution was added to a pan containing a mixture of decyl norbornene (1.63g) and trimethoxysilyl norbornene (0.37g), heated to 130 deg.C, and the resulting mixture formed a gel in 4 minutes. After 1 hour, a solid block was obtained. A sample of the solution was also heated from room temperature to 300 ℃ at a rate of 10 ℃/min, and Δ H and peak temperature were measured with a Differential Scanning Calorimeter (DSC). Results of the DSC test: Δ H200.8J/g; the peak temperature was 89.0 ℃.

Example 75

trans-[Pd(CH₃)(P(i-Pr)₃)₂(NCCH₃)][FABA]

Is full of N₂Stirring gray Pd (CH)₃)Cl(PⁱPr₃)₂(0.29g, 0.61mmol) of CH₃CN (20mL) suspension with addition of Ag (toluene)₂[B(C₆F₅)₄](0.59g, 0.61mmol) of CH₃CN solution (10mL), clear immediately and regenerate grey solid. The suspension was stirred for 15 minutes and then filtered through a 0.45 μm Teflon filter and the pale yellow filtrate was concentrated to dryness to giveTo an off-white foam. Yield: 0.43g (62%).³¹P NMR(CD₂Cl₂)δ＝40.2ppm。

Pyrolysis test

Example 76

trans-[Pd(OAc)(P(R)₃)₂(MeCN)][B(C₆F₅)₄](R＝Cy，i-Pr)

Trans- [ Pd (OAc)) (P (Cy) in Wilmad Young valve NMR tube (tubes 75A and 75B, respectively)₃)₂(MeCN)][B(C₆F₅)₄](26.5mg, 0.0183mmol) and trans- [ Pd (OAc) (P (i-Pr)₃)₂(MeCN)][B(C₆F₅)₄](22.2mg, 0.0184mmol) in C₆D₆(0.6 mL). The contents of each NMR tube were heated to 58-62 deg.C, cooled to room temperature, and recorded after a time interval of 3 and 18 hours³¹P and¹h NMR. Tubes 75A and 75B contain a hydride of each pro-initiator, demonstrating that the title pro-initiator is pyrolyzed to produce palladium hydride.

Example 77

Production of cis- [ (P (i-Pr) in situ₃)Pd(κ²-P，C-P(i-Pr₂)CMe₂)(CD₃CN)][B(C₆F₅)₄]

Reaction of the Complex [ Pd (kappa)]in air²-O，O′-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄](55mg, 47. mu. mol) in acetonitrile-d₃(0.79mL) and stored in the same solvent until³¹P NMR spectrum showed end of cyclometalation. Acetonitrile-d was then removed under vacuum₃An oil is obtained. NMR of the oil (C: (M))¹H and³¹p) Spectroscopy showed the presence of starting material and cis- [ (P (i-Pr) in about 70 and 30% yields₃)Pd(κ²-P，C-P(i-Pr₂)CMe₂)(CD₃CN)][B(C₆F₅)₄]. Thus, from [ Pd (κ)²-O，O′-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄]The formation of the metallization may occur under mild temperatures and conditions. Similarly, dissolve in d₈[ Pd (. kappa.) of THF²-O，O′-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄]At 1 equivalent CH₃Conversion to cis- [ (P (i-Pr) in the presence of CN at room temperature₃)Pd(κ²-P，C-P(i-Pr₂)CMe₂)(CD₃CN)][B(C₆F₅)₄]。

Example 78

trans-[Pd(P(i-Pr)₃)₂(OAc)(MeCN)][B(C₆F₅)₄]Pyrolysis of

Reacting trans- [ Pd (P (i-Pr) under nitrogen₃)₂(OAc)(MeCN)][B(C₆F₅)₄](40mg) in dried and deoxygenated tetrahydrofuran-d₈(0.79 mL). The tube is then heated at 55 ℃ and passed³¹The P NMR spectrum was continuously monitored for 120 minutes for the pyrolysis reaction. Through the reaction process, trans- [ Pd (P (i-Pr)₃)₂(OAc)(MeCN)][B(C₆F₅)₄]Disappearance of the signal, with concomitant generationThe signal attributable to the mixed palladium hydride species that generated E, F and G in FIG. 1. In addition, transient intermediates [ Pd (kappa)]are produced²-O，O′-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄](<2%) (C in FIG. 1, example 13) and trans- [ Pd (CH)₃)(P(i-Pr)₃)₂(NCCH₃)][FABA](. ltoreq.15%) (I in FIG. 1, (example 74)). trans- [ Pd (P (i-Pr)₃)₂(OAc)(MeCN)][B(C₆F₅)₄]The total conversion to hydride (E, F and G) mixture was about 50%.

Example 79

cis-[(P(i-Pr)₃)Pd(κ²-P，C-P(i-Pr₂)CMe₂)(CD₃CN)][B(C₆F₅)₄]To trans- [ (P (i-Pr)₃(P-i-Pr₂(isopropenyl) Pd (H) (MeCN)][B(C₆F₅)₄]Transformation of (2)

Under nitrogen, the complex cis- [ (P (i-Pr)₃)Pd(κ²-P，C-P(i-Pr₂)CMe₂)(CD₃CN)][B(C₆F₅)₄](40mg) in chloroform-d₃(1 mL). At room temperature, the complex is quantitatively converted from the starting material into the new hydride trans- [ (P (i-Pr)₃(P(i-Pr)₂(isopropenyl) Pd (H) (MeCN)][B(C₆F₅)₄](³¹P{¹H)NMR(CDCl₃) δ 52.53 and 46.45(Jp-p ═ 320Hz)) (complex E in fig. 1), proton NMR showed AB pattern at δ -15.25ppm and new ethylene-like resonance in the 5.90 to 5.60 region, demonstrating generation of tethered isopropenyldiisopropylphosphine ligands by elimination of β -hydride to generate propenyl³¹P and¹resonance broadening in the H spectrum indicates that phosphine exchange is occurring. The intensity of the Pd-H resonance (ca. delta. 15.2ppm) signal remained unchanged during the experiment, indicating no loss of the product.

Example 80

[Pd(κ²-O，O′-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄]Conversion to cationic palladium hydride species

The complex [ Pd (kappa.) was reacted under nitrogen²-O，O′-OAc)(P(i-Pr)₃)₂][B(C₆F₅)₄](40mg) in tetrahydrofuran-d containing 1 equivalent of acetonitrile₈(1 mL). Heating the solution to 55 ℃ and passing it³¹The reaction was monitored by P NMR and the appearance of cis- [ Pd (. kappa.) was observed²-P，C-P(i-Pr)₂(C(CH₃)₂)(P(i-Pr)₃)(MeCN)][B(C₆F₅)₄]And the mixture was converted to a mixture of palladium hydride species E, F and G in figure 1 in about 50% yield after 180 minutes. The product is characterized by a Pd-H resonance with a monophosphoric signal at delta 56.8ppm (single peak) and a monophosphoric signal at delta 56.8ppm (single peak)A broad proton signal of delta-15.2 ppm.

Example 81

[Pd(O₂CCMe₃)(P(i-Pr)₃)₂(NCCH₃)][B(C₆F₅)₄]Conversion to cationic palladium hydride species

The complex [ Pd (O) is reacted under nitrogen₂CCMe₃)(P(i-Pr)₃)₂(NCCH₃)][B(C₆F₅)₄](40mg) in tetrahydrofuran-d₈(1 mL). Heating the solution to 55 ℃and passing it³¹The reaction was monitored by P NMR. During 180 minutes of heating, [ Pd (kappa.)]is observed to appear²-O，O’-CMe₃)(P(i-Pr)₃)₂][B(C₆F₅)₄]And the mixture was totally converted to a mixture of palladium hydride species E, F and G in figure 1 with a yield of about 55%. The product is characterized by a Pd-H resonance with a monophosphoric signal at delta 56.2ppm (single peak) and a broad proton signal at delta-15.4 ppm.

Examples 82a and 82b

Comparison of incubation periods of pyridine-and acetonitrile-loaded proinitiators

Two vials were charged with an 80: 20 (mol%) mixture of decyl norbornene and trimethoxysilyl norbornene (2g, 8.7mmol) and a magnetic stir bar, respectively. To the first vial (vial 82a) was added [ Pd (P-i-Pr)₃)₂(OAc)(MeCN)][B(C₆F₅)₄](Pd 1206；0.4mg，3.5×10^-7mol) of CH₂Cl₂The solution (100. mu.L) was added to the other bottle (bottle 82b) [ Pd (P-i-Pr)₃)₂(OAc)(NC₅H₅)][B(C₆F₅)₄](0.4mg，3.5×10^-7mol) of CH₂Cl₂Solution (100. mu.L). Both bottles were sealed and stirred at ambient temperature (21 ℃). After 70 hours, example 82a was much more viscous than example 82 b. The sample from each vial was also heated from room temperature to 300 ℃ at a rate of 10 ℃/min, and Δ H, the onset reaction temperature, and the peak temperature were measured using a Differential Scanning Calorimeter (DSC). The residue of each sample was cured to a solid mass by being left in an oven at 130 ℃ for 1 hour.

Examples	Reaction temperature (. degree.C.) to start reaction	ΔH(J/g)	Peak temperature (. degree. C.)
				82a	68	216.8	109.8
82b	88	195.0	126.3

This comparative example demonstrates that selection of a suitable lewis base can extend the shelf life of the formulation.

Examples 83a and 83b

Comparison of incubation periods for pyridine-and acetonitrile-loaded premetallization initiators

Two vials each were charged with decyl norbornene and trimethoxysilyl norbornene80: 20 (mol%) mixture (2g, 8.7mmol) and a magnetic stir bar. To the first bottle(bottle 83a) was added [ (P-i-Pr)₃)Pd(κ²-P，C-P-i-Pr₂CMe₂)(NC₅H₅)][B(C₆F₅)₄](0.4mg，3.5×10^-7mol) of CH₂Cl₂The solution (100. mu.L) was added to the flask (83 b) [ (P-i-Pr)₃)Pd(κ²-P，C-P-i-Pr₂CMe₂)(CH₃CN)][B(C₆F₅)₄](0.4mg，3.5×10^-7mol) of CH₂Cl₂Solution (100. mu.L). Both bottles were sealed and stirred at ambient temperature (21 ℃). After 23 hours, example 83b was much more viscous than example 83 a. After 70 hours, example 83b was almost non-flowable and example 83a was free-flowing. The sample from each vial was also heated from room temperature to 300 ℃ at a rate of 10 ℃/min, and Δ H, the onset reaction temperature, and the peak temperature were measured using a Differential Scanning Calorimeter (DSC). The residue of each sample was cured to a solid mass by being left in an oven at 130 ℃ for 1 hour.

Examples	Reaction temperature (. degree.C.) to start reaction	ΔH(J/g)	Peak temperature (. degree. C.)
				83a	82	226.2	139.9
83b	38	232.5	114.3

This comparative example demonstrates that selection of a suitable lewis base can extend the shelf life of the formulation.

It should be appreciated by now that the embodiments according to the present invention have been described as advantageous one-component latent catalyst systems (i.e. one-component pro-initiators in monomer that can be triggered to start substantial polymerization). Furthermore, it should be appreciated that embodiments according to the present invention have been described that also provide methods of forming such single component latent catalyst systems, and that the catalyst systems are suitable for bulk and solution polymerization.

It can also be seen that embodiments of the catalyst system of the present invention have significant advantages over currently known two-part systems for bulk polymerization in that: these systems do not require mixing of multiple parts (especially examples 44-47) and can be formulated without significant viscosity change over longer periods of time (especially example 51). In addition, such one-component systems do not suffer from the difficulties associated with formulating the two separate parts, the errors in mixing those parts before use, and the potential for excessive waste caused by the expiration of the mix before the amount of mixing is consumed. It can also be seen that the use of a separable latent pro-initiator in a solvent polymerization system is advantageous (especially examples 36-39). For example, such a separable pro-initiator can be prepared in large quantities to reduce production costs, and its activity can be measured before it is used to initiate polymerization to ensure the required conversion without using an excess of initiator to reduce the cost of the desired polymer. Furthermore, such one-component pro-initiators allow better control of the metering polymerization. Thus, there is a need for such a one-component latent pro-initiator system to provide at least the above-mentioned advantages.

Finally, it will be appreciated that the catalyst system according to the present invention is suitable for use in the preparation of polymers for a wide variety of applications and/or uses. Such applications include, but are not limited to, microelectronic, optoelectronic, and optical applications, but also include molded and otherwise shaped structures and/or devices wherein at least a portion of the structure/device is formed from a polymer utilizing the catalyst system of the present invention.

Such microelectronic applications/uses include, but are not limited to, dielectric films (i.e., multichip modules and flexible circuits), die attach adhesives, underfill adhesives, die encapsulants, glob tops, tight sealing plates and die protective coatings, embedded passives, laminating adhesives, capacitor dielectrics, high frequency insulators/connectors, high voltage insulators, high temperature cable coatings, conductive adhesives, reusable adhesives, photosensitive adhesives and dielectric films, resistors, inductors, capacitors, antennas, and printed circuit board substrates. As is known in the art and literature, the definition of chip includes "integrated circuits" or "small pieces of semiconductor material constituting the substrate of an integrated circuit", Mirriam Webster's Collegiate Dictionary, 10th Ed, 1993, Merriam-Webster, Inc., Springfield, MA, USA. Thus, the above-mentioned electronic applications such as multi-chip modules, chip encapsulants, chip protective coatings, and the like, relate to semiconductor substrates or components and/or integrated circuits containing the optical polymers of the present invention encapsulated and coated thereon. The optical coating or encapsulant is part of an optical semiconductor element as a covering or packaging material for a chip or integrated circuit or semiconductor.

In optical applications, uses include, but are not limited to, optical films, lenses, waveguides, optical fibers, photosensitive optical films, specialty lenses, windows, high index films, laser optics, color filters, optical adhesives, and optical connectors. Other optical applications include the use of the above copolymers as coatings and encapsulants for various types of light sensitive elements, including but not limited to Charge Coupled Device (CCD) image sensors, and Complementary Metal Oxide Semiconductor (CMOS) and imaging CMOS (imos), among others. IMOS can be used to seal arrays of chips and semiconductors, etc. As is known in the art and literature, a sensor can be generally described as a device having an optical element in the path of a light source that transmits light to a converter to convert the pattern, color, etc. of the light into an electronic signal that can be transmitted and stored on a processor or computer. Other end uses include sensors for cameras (e.g., web and digital cameras) and surveillance, etc., sensors for telescopes, microscopes, various infrared monitors, bar code readers, digital electronic secretaries, image scanners, digital video conferencing, cellular phones, and electronic toys, etc. Other sensor applications include various biometric devices such as iris scanners, retina scanners, fingerprint scanners, and the like.

Other optical applications include various light emitting diodes coated, encapsulated, etc. with the optical cyclic olefin polymers. Typical LEDs include visible light LEDs, white light LEDs, ultraviolet light LEDs, laser LEDs, and the like. These LEDs are useful in automotive lighting systems, backlights for displays, general lighting, bulb replacements, and traffic lights, among others.

Claims (64)

1. A composition comprising a palladium compound of formula Ia or Ib:

[(E(R)₃)_aPd(Q)(LB)_b]_p[WCA]_r(Ia)

[(E(R)₃)(E(R)₂R^*)Pd(LB)]_p[WCA]_r(Ib)

wherein E (R)₃Is a group 15 neutral electron donor ligand wherein E is selected from the group consisting of group 15 elements of the periodic Table of the elements, and each R independently represents hydrogen, deuterium, or an anionic hydrocarbyl containing moiety; r^*Is a moiety containing an anionic hydrocarbyl group bonded to Pd and having β hydrogens relative to Pd, Q is an anionic ligand selected from the group consisting of carboxylate, thiocarboxylate, and dithiocarboxylate groups, LB is a Lewis base, WCA represents a weakly coordinating anion, a represents an integer of 1, 2, or 3, b represents an integer of 0, 1, or 2, wherein the sum of a + b is 1, 2, or 3, p andr is an integer suitably selected to balance the charge of the compound.

2. The palladium compound of claim 1, where E is phosphorus (P), arsenic (As), antimony (Sb), or bismuth (Bi).

3. The palladium compound of claim 1, where each R is independently linear and branched (C)₁-C₂₀) Alkyl, (C)₃-C₁₂) Cycloalkyl group, (C)₂-C₁₂) Alkenyl, (C)₃-C₁₂) Cycloalkenyl group, (C)₅-C₂₀) Polycyclic alkyl radical, (C)₅-C₂₀) Polycyclic alkenyl radical or (C)₆-C₁₂) And (4) an aryl group.

4. The palladium compound of claim 3, wherein R is monodentate, symmetrically bidentate, asymmetrically chelated bidentate, asymmetrically bridged, symmetrically bridged, or a combination thereof.

5. The palladium compound of claim 1, where E is phosphorus (P) or arsenic (As), and each R is linear and branched (C)₁-C₂₀) Alkyl, (C)₃-C₁₂) Cycloalkyl group, (C)₂-C₁₂) Alkenyl, (C)₃-C₁₂) Cycloalkenyl group, (C)₅-C₂₀) Polycyclic alkyl radical, (C)₅-C₂₀) Polycyclic alkenyl radical or (C)₆-C₁₂) And (4) an aryl group.

6. The palladium compound of claim 5, wherein R^*Is straight-chain or branched (C)₂-C₂₀) Alkyl, (C)₃-C₁₂) Cycloalkyl group, (C)₂-C₁₂) Alkenyl, (C)₃-C₁₂) Cycloalkenyl group, (C)₅-C₂₀) Polycyclic alkyl radical or (C)₅-C₂₀) A polycyclic alkenyl group.

7. The palladium compound of claim 1, where E is selected from the group consisting of phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi), and each R is independently selected from the group consisting of linear and branched (C)₁-C₂₀) Alkyl, (C)₃-C₁₂) Cycloalkyl group, (C)₂-C₁₂) Alkenyl, (C)₃-C₁₂) Cycloalkenyl group, (C)₅-C₂₀) Polycyclic alkyl radical, (C)₅-C₂₀) Polycyclic alkenyl radical and (C)₆-C₁₂) Anionic hydrocarbyl containing moiety of an aryl radical, R^*Is straight-chain or branched (C)₁-C₂₀)Alkyl, (C)₃-C₁₂) Cycloalkyl group, (C)₂-C₁₂) Alkenyl, (C)₃-C₁₂) Cycloalkenyl group, (C)₅-C₂₀) Polycyclic alkyl radical or (C)₅-C₂₀) A polycyclic alkenyl group.

8. The palladium compound of claim 1, where the neutral electron donor ligand E (R)₃) Is di-tert-butylcyclohexylphosphine, dicyclohexyl-tert-butylphosphine, tricyclohexylphosphine, tricyclopentylphosphine, dicyclohexyladamantylphosphine, cyclohexyldiadamantylphosphine, triisopropylphosphine, di-tert-butylisopropylphosphine, or diisopropyl-tert-butylphosphine.

9. The palladium compound of claim 1, where the neutral electron donor ligand E (R)₃) Is tri-n-propylphosphine, tri-tert-butylphosphine, di-n-butyladamantylphosphine, dinorbornylphosphine, tert-butyldiphenylphosphine, isopropyldiphenylphosphine, dicyclohexylphenylphosphine, di-tert-butylisopropylphosphine, diisopropyltert-butylphosphine, di-tert-butylneopentylphosphine, or dicyclohexylneopentylphosphine.

10. The palladium compound of claim 1, where the neutral electron donor ligand E (R)₃) Is trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-butylphosphine, tri-sec-butylphosphine, triisobutylphosphine, tricyclopropylphosphine, tricyclobutylphosphine, tricycloheptylphosphine, isopropenyldiisopropylphosphine, cyclopentenyldicyclopropenylphosphine, cyclohexenyldicyclohexylphosphine, triphenylphosphine, trinaphthylphosphine, tribenzylphosphine, benzyldiphenylphosphine, di-n-butyladamantylphosphine, allyldiphenylphosphine, vinyldiphenylphosphine, cyclohexyldiphenylphosphine, di-tert-butylphenyl phosphine, diethylphenylphosphine,Dimethylphenylphosphine; diphenylpropylphosphine, ethyldiphenylphosphine, tri-n-octylphosphine, tribenzylphosphine, 4, 8-dimethyl-2-phosphabicyclo [ 3.3.1%]Nonane or 2, 4, 6-triisopropyl-1, 3-dioxa-5-phosphane.

11. The palladium compound of claim 1, where the neutral electron donor ligand E (R)₃) Is tricyclohexylarsine, tricyclopentylarsine, di-tert-butylcyclohexylarsine, dicyclohexyl-tert-butylarsine, triisopropylarsine, di-tert-butylisopropylarsine, or diisopropyl-tert-butylarsine.

12. The palladium compound of claim 1, where the neutral electron donor ligand E (R)₃) Is dicyclohexyladamantylcarsine, cyclohexyldiadamantylarsine, di-n-butyladamantylarsine, dinorbonylarsine, tert-butyldiphenylarsine, isopropyldiphenylarsine, dicyclohexylphenylarsine, or dicyclohexylneopentylgarsine.

13. The palladium compound of claim 1, where the neutral electron donor ligand E (R)₃) Is trimethyl arsine, triethyl arsine, tri-n-propyl arsine, triisopropyl arsine, tri-n-butyl arsine, tri-sec-butyl arsine, triisobutyl arsine, tri-tert-butyl arsine, tricyclopropyl arsine, tricyclobutyl arsine, tricycloheptyl arsine, tri-tert-butyl arsine,isopropenyldiisopropylarsine, cyclopentenyldicyclopropenylarsine, cyclohexenyldicyclohexylarsine, triphenylarsine, trinaphthylarsine, tribenzylarsine, benzyldiphenylarsine, allyldiphenylarsine, vinyldiphenylarsine, cyclohexyldiphenylarsine, di-t-butylphenyl arsine, diethylphenylarsine, dimethylphenylarsine, diphenylpropylarsine, ethyldiphenylarsine, tri-n-octylarsine, tribenzylarsine, di-t-butylisopropylarsine, diisopropyl-t-butylarsine, or di-t-butylneopentyl arsine.

14. The palladium compound of claim 1, where the neutral electron donor ligand E (R)₃) Is tricyclohexyl, di-tert-butylcyclohexyl, cyclohexyl di-tert-butyl, triisopropyl, di-tert-butylisopropyl or diisopropyl tert-butylButyl _.

15. The palladium compound of claim 1, where the neutral electron donor ligand E (R)₃) Is dicyclohexyladamantyl, cyclohexyldiamantanyl, dicyclohexylt-butyl, dinorbornyl, t-butyldi (t-butyldiistidine), isopropyldiphenyl, dicyclohexylphenyl, or dicyclohexylneopentyl.

16. The palladium compound of claim 1, where the neutral electron donor ligand E (R)₃) Are trimethyl-, triethyl-, tri-n-propyl-, triisopropyl-, tri-n-butyl-, tri-sec-butyl-, triisobutyl-, tri-tert-butyl-, tricyclopropyl-, tricyclobutyl-, tricyclopentyl-, tricycloheptyl-, isopropenyl-diisopropyl-, cyclopentenylbicyclopentyl-, cyclohexenyldicyclohexyl-, triphenyl-, trinaphthyl-, tribenzyl-, benzyldiphenyl-, di-n-butyladamantyl-, dinonyl-, tert-butyldiphenyl-, allyldiphenyl-, vinyldiphenyl-, cyclohexyldiphenyl-, di-tert-butylphenyl-, diethylphenyl-, dimethylphenyl-, diphenylphenyl-, ethyldiphenyl-, tri-n-octyl-, tribenzyl-, di-tert-butylisopropyl-, diisopropyl-tert-butyl-, or di-tert-butylneopentyl.

17. The palladium compound of claim 1, where the neutral electron donor ligand E (R)₃) Is tricyclohexyl

Or diisopropyl tert-butyl

18. The palladium compound of claim 1, where the neutral electron donor ligand E (R)₃) Is dicyclohexyladamantyl

Cyclohexyl diamantanyl

Dicyclohexyl tert-butyl

Di-norbornyl

Tert-butyl di(t-butylbismuthine), isopropyldiphenyl

Dicyclohexylphenyl

Di-tert-butyl isopropyl

Diisopropyl tert-butyl

Or dicyclohexylneopentyl group

19. The palladium compound of claim 1, where the neutral electron donor ligand E (R)₃) Is threeMethylbismuth, triethylbismuth, tri-n-propylbismuth, triisopropylbismuth, tri-n-butylbismuth, tri-sec-butylbismuth, triisobutylbismuth, tri-tert-butylbismuth, di-tert-butylcyclohexylbismuth, dicyclohexyltert-butylbismuth, tricyclopropylbuthium, tricyclobutylbuthium, tricyclopentylbismuth, tricyclohexylbismuth, isopropenyldiisopropylbismuth, cyclopentenylbicyclopropylenylbutylkynylbutylkylbutylkylbutylkylbutylkylbutylkylbutylkylbutylkylbutylkylbutylkyium, cyclohexenyldicyclohexylbismuth, triphenylbismuth, trinaphthenylbismuth, tribenzyldiphenylbismuth, benzyldiphenylbismuth, dicyclohexyladamantylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbutylbuty, Isopropyldiphenylbismuth, dicyclohexylphenylbismuth, tribenzylbismuth, di-t-butylisopropylbismuth, diisopropyl-t-butylbismuth, di-t-butylneopentyl bismuth, dicyclohexylneopentyl bismuth, tris (4-methoxyphenyl) bismuth, tris (2-methylphenyl)

And tris (4-fluorophenyl)

20. The palladium compound of claim 1, wherein Q is a carboxylate anion represented by the formula:

wherein R is¹Independently hydrogen, straight and branched C₁-C₂₀Alkyl radical, C₁-C₂₀Haloalkyl, substituted and unsubstituted C₃-C₁₂Cycloalkyl, substituted and unsubstituted C₂-C₁₂Alkenyl, substituted and unsubstituted C₃-C₁₂Cycloalkenyl, substituted and unsubstituted C₅-C₂₀Polycycloalkyl, substituted and unsubstituted C₆-C₁₄Aryl, and substituted or unsubstituted C₇-C₂₀An aralkyl group.

21. The palladium compound of claim 20, where R¹Is methyl, trifluoromethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, neopentyl, cyclohexyl, norbornyl, adamantyl, phenyl, pentafluorophenyl or benzyl.

22. The palladium compound of claim 21, where Q is CH₃CO₂ ^-Or Me₃CCO₂ ^-。

23. The palladium compound of claim 21, where Q is CF₃CO₂ ^-、C₆H₅CO₂ ^-、C₆H₅CH₂CO₂ ^-Or C₆F₅CO₂ ^-。

24. The palladium compound of claim 21, where Q is CH₃C(S)O^-、CH₃C(S)₂ ^-、CF₃C(S)O^-、CF₃C(S)₂ ^-、Me₃CC(S)O^-、Me₃CC(S)₂ ^-、C₆H₅C(S)O^-、C₆H₅C(S)₂ ^-、C₆H₅CH₂(S)O^-、C₆H₅CH₂(S)₂ ^-、C₆F₅C(S)O^-Or C₆F₅C(S)₂ ^-。

25. The palladium compound of claim 5 or 6, wherein Q is a carboxylate anion represented by the formula:

wherein R is¹Independently hydrogen, straight and branched C₁-C₂₀Alkyl radical, C₁-C₂₀Haloalkyl, substituted and unsubstituted C₃-C₁₂Cycloalkyl, substituted and unsubstituted C₂-C₁₂Alkenyl, substituted and unsubstituted C₃-C₁₂Cycloalkenyl, substituted and unsubstituted C₅-C₂₀Polycycloalkyl, substituted and unsubstituted C₆-C₁₄Aryl, and substituted or unsubstituted C₇-C₂₀An aralkyl group.

26. The palladium compound of claim25, where R¹Is methyl, trifluoromethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, neopentyl, cyclohexyl, norbornyl, adamantyl, phenyl, pentafluorophenyl or benzyl.

27. The palladium compound of claim 26, where Q is CH₃CO₂ ^-Or Me₃CCO₂ ^-。

28. The palladium compound of claim 26, where Q is CF₃CO₂ ^-、C₆H₅CO₂ ^-、C₆H₅CH₂CO₂ ^-Or C₆F₅CO₂ ^-。

29. The palladium compound of claim 26, where Q is CH₃C(S)O^-、CH₃C(S)₂ ^-、CF₃C(S)O^-、CF₃C(S)₂ ^-、Me₃CC(S)O^-、Me₃CC(S)₂ ^-、C₆H₅C(S)O^-、C₆H₅C(S)₂ ^-、C₆H₅CH₂(S)O^-、C₆H₅CH₂(S)₂ ^-、C₆F₅C(S)O^-Or C₆F₅C(S)₂ ^-。

30. The palladium compound of claim 1, wherein the lewis base is water, dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, acetone, benzophenone, acetophenone, methanol, isopropanol, benzonitrile, adamantanecarbonitrile, tert-butylnitrile, tert-butyl isocyanide, xylyl isocyanide, dimethylaminopyridine, 4-dimethylaminopyridine, tetramethylpyridine, 4-methylpyridine, tetramethylpyrazine, triisopropyl phosphite, triphenyl phosphite, or triphenylphosphine oxide.

31. The palladium compound of claim 1, where the lewis base is acetonitrile, pyridine, 2, 6-lutidine, 2, 6-dimethylpyrazine, or pyrazine.

32. The palladium compound of claim 1, wherein the lewis base is dioxane, acetone, benzophenone, acetophenone, methanol, isopropanol, triethylamine, dimethylaniline, N-neopentylidenemethane, 1-dimethyl-N-neopentylidenemethamine, N-methyltrimethylacetamide, N-methyl-cyclohexanamide, dimethylaminopyridine, tetramethylpyrazine, and triphenyl phosphite.

33. The palladium compound of claim 1, where the weakly coordinating anion is a borate, aluminate, or triflimide (triflimide) anion.

34. The palladium compound of claim 33, where the weakly coordinating anion is a borate or aluminate of the formula:

[M(R¹⁰)(R¹¹)(R¹²)(R¹³)]OR [ M (OR)]¹⁴)(OR¹⁵)(OR¹⁶)(OR¹⁷)]

Wherein M is boron or aluminum, R¹⁰、R¹¹、R¹²And R¹³Independently represent fluorine, linear and branched C₁-C₁₀Alkyl, straight and branched C₁-C₁₀Alkoxy, straight and branched C₃-C₅Haloalkenyl, straight and branched C₃-C₁₂Trialkylsiloxy radical, C₁₈-C₃₆Triarylsiloxy, substituted and unsubstituted C₆-C₃₀Aryl, and substituted and unsubstituted C₆-C₃₀Aryloxy group, wherein R¹⁰To R¹³Cannot simultaneously represent alkoxy or aryloxy, and is in R¹⁰To R¹³When it is a substituted aryl or aryloxy group, the group may be mono-or polysubstituted, wherein the substituents are independently straight-chain and branched C₁-C₅Alkyl, straight and branched C₁-C₅Haloalkyl, straight and branched C₁-C₅Alkoxy, straight and branched C₁-C₅Haloalkoxy, straight and branched C₁-C₁₂Trialkylsilyl group, C₆-C₁₈Triarylsilyl, chloro, bromo, iodo and fluoro; r¹⁴、R¹⁵、R¹⁶And R¹⁷Independently of each other straight-chain and branched C₁-C₁₀Alkyl, straight and branched C₁-C₁₀Haloalkyl, C₂-C₁₀Haloalkenyl, substituted and unsubstituted C₆-C₃₀Aryl, and substituted and unsubstituted C₇-C₃₀Aralkyl radical, with the proviso that R¹⁴To R¹⁷At least three of which contain halogen-containing substituents, and when R is¹⁴To R¹⁷When it is a substituted aryl or aryloxy group, the radicalThe radicals may be mono-or polysubstituted, where the substituents are straight-chain and branched C₁-C₅Alkyl, straight and branched C₁-C₅Haloalkyl, straight and branched C₁-C₅Alkoxy, straight and branched C₁-C₁₀Haloalkoxy, chloro, bromo and fluoro, and OR¹⁴And OR¹⁵May together form a structure represented by-O-R¹⁸A chelating substituent represented by-O-, wherein an oxygen atom is bonded to M, and R¹⁸Is a divalent radical such as substituted and unsubstituted C₆-C₃₀Aryl and substituted and unsubstituted C₇-C₃₀An aralkyl group.

35. The Weakly Coordinating Anion (WCA) of claim 34, wherein when M is boron, the WCA is tetrakis (pentafluorophenyl) borate or tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate.

36. The Weakly Coordinating Anion (WCA) of claim 34, wherein when M is boron, the WCA is tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate, tetrakis (3, 4, 5, 6-tetrafluorophenyl) borate, tetrakis (1, 2, 2-trifluorovinyl) borate, tetrakis (4-triisopropylsilyltetrafluorophenyl) borate, tetrakis (4-dimethyltert-butylsilyltetrafluorophenyl) borate, tetrakis [3, 5-bis [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl]phenyl]borate, tetrakis [3- [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl]-5- (trifluoromethyl) phenyl]borate, or tetrakis [3- [2, 2, 2-trifluoro-1- (2, 2, 2-trifluoroethoxy) -1- (trifluoromethyl) ethyl]-5- (trifluoromethyl) phenyl]borate.

37. The Weakly Coordinating Anion (WCA) of claim 34, wherein when M is boron, the WCA is tetrakis (2-fluorophenyl) borate, tetrakis (3-fluorophenyl) borate, tetrakis (4-fluorophenyl) borate, tetrakis (3, 5-difluorophenyl) borate, tetrakis (3, 4, 5-trifluorophenyl) borate, methyltris (perfluorophenyl) borate, ethyltris (perfluorophenyl) borate, phenyltris (perfluorophenyl) borate, (triphenylsiloxy) tris (pentafluorophenyl) borate, (octyloxy) tris (pentafluorophenyl) borate, tetrakis [3, 5-bis [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl]phenyl]borate, tetrakis [3- [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl]-5- (trifluoromethyl) borate ) Phenyl]borate or tetrakis [3- [2, 2, 2-trifluoro-1- (2, 2, 2-trifluoroethoxy) -1- (trifluoromethyl) ethyl]-5- (trifluoromethyl) phenyl]borate.

38. The Weakly Coordinating Anion (WCA) of claim 34, wherein when M is aluminum, the WCA is tetrakis (pentafluorophenyl) aluminate or tetrakis (3, 5-bis (trifluoromethyl) phenyl) aluminate.

39. The Weakly Coordinating Anion (WCA) of claim 34, wherein when M is aluminum, the WCA is tris (perfluorobiphenyl) fluoroaluminate, (octyloxy) tris (pentafluorophenyl) aluminate, or methyltris (pentafluorophenyl) aluminate.

40. The Weakly Coordinating Anion (WCA) of claim 34, wherein divalent radical R¹⁸Represented by the following structure:

wherein each R¹⁹Independently hydrogen, straight and branched C₁-C₅Alkyl, straight and branched C₁-C₅Haloalkyl, chlorine, bromine and fluorine; r²⁰Is a single substituent or up to four per aromatic ring, independently hydrogen, straight and branched chain C, depending on the valences available on each ring carbon atom₁-C₅Alkyl, aryl, heteroaryl, and heteroaryl,Straight and branched C₁-C₅Haloalkyl, straight and branched C₁-C₅Alkoxy, straight and branched C₁-C₁₀Haloalkoxy, chloro, bromo, and fluoro; and each s independently represents an integer of 0 to 6.

41. The Weakly Coordinating Anion (WCA) of claim 40, wherein when s is 0, -O-R¹⁸-O-comprises 2, 3, 4, 5-tetrafluorobenzenediol (-OC)₆F₄O-), 2, 3, 4, 5-tetrachlorobenzenediol (-OC)₆Cl₄O-)、2，3, 4, 5-tetrabromobenzene diphenol (-OC)₆Br₄O-), and bis (1, 1 '-bis-tetrafluorophenyl-2, 2' -diphenol).

42. The palladium compound of claim 33, where the weakly coordinating anion is bis (trifluoromethanesulfonyl) imide, triflimide ([ N (S (O))₂C₄F₉)₂]^-) Bis (pentafluoroethanesulfonyl) imide ([ N (S (O))₂C₂F₅)₂]^-) Or 1, 1, 2, 2, 2-pentafluoroethane-N- [ (trifluoromethyl) sulfonyl group]Sulfonamide ([ N (S (O))₂CF₃)(S(O)₂C₄F₉)]^-)。

43. The palladium compound of claim 1, wherein the weakly coordinating anion is tris (trifluoromethanesulfonyl) methane anion ([ C (S (O))₂CF₃)₃]^-)。

44. The palladium compound of claim 1, wherein [ (E (R))₃)_aPd(Q)(LB)_b]_p[WCA]Is [ Pd (OAc)) (P (Cy)₃)₂(MeCN)][B(C₆F₅)₄]、

[Pd(OAc)(P(Cy)₂(CMe₃))₂(MeCN)][B(C₆F₅)₄]、

[Pd(OAc)(P(i-Pr)(CMe₃)₂)₂(MeCN)][B(C₆F₅)₄]、

[Pd(OAc)₂(P(i-Pr)₂(CMe₃))₂(MeCN)][B(C₆F₅)₄]、

[Pd(OAc)(P(i-Pr)₃)₂(MeCN)][B(C₆F₅)₄]、

[Pd(O₂C-t-Bu)(P(Cy)₃)₂(MeCN)][B(C₆F₅)₄]、

[Pd(O₂C-t-Bu)(P(Cy)₂(CMe₃))₂(MeCN)][B(C₆F₅)₄]、

[Pd(O₂C-t-Bu)₂(P(i-Pr)₂(CMe₃))₂、

[Pd(O₂C-t-Bu)(P(i-Pr)₃)₂(MeCN)][B(C₆F₅)₄]。

45. The palladium compound of claim 1, wherein [ (E (R))₃)_aPd(Q)(LB)_b]_pIs [ Pd (OAc)) (P (Cp)₃)₂(MeCN)][B(C₆F₅)₄]、[Pd(OAc)(P(i-Pr)₂(CMe₃))₂(MeCN)][B(C₆F₅)₄]、[Pd(O₂C-t-Bu)(P(Cp)₃)₂(MeCN)][B(C₆F₅)₄]、[Pd(O₂C-t-Bu₂(P(i-Pr)(CMe₃)₂)(MeCN)][B(C₆F₅)₄]、[Pd(O₂C-t-Bu)(P(i-Pr)₂(CMe₃))₂(MeCN)][B(C₆F₅)₄]、cis-[Pd(P(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(NC₅H₅)][B(C₆F₅)₄]、cis-[Pd(P(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(2，6-Me₂py)][B(C₆F₅)₄]And cis- [ Pd (P (i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(2，6-Me₂pyz)][B(C₆F₅)₄]。

46. The palladium compound of claim 1, wherein [ (E (R))₃)_aPd(Q)(LB)_b]_pIs [ (P (Cy))₃)₂Pd(κ²-O，O’-O₂CCH₃)][B(C₆F₅)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂C-t-Bu)][B(C₆F₅)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂CC₆H₅)][B(C₆F₅)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂CC₆F₅)][B(C₆F₅)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂CCF₃)][B(C₆F₅)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂CCH₃)][B(C₆H₃-3，5-(CF₃)₂)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂CCH₃)][Al(OC(CF₃)₂C₆H₄CH₃)₄]、[(P(Cy)₃)₂Pd(κ²-O，O’-O₂CPh)][B(C₆F₅)₄]、[(P(Cy-d₁₁)₃)₂Pd(κ²-O，O-OAc)][B(C₆F₅)₄]、[Pd(P(i-Pr)₃)₂(κ²-O，O’-O₂CCH₃)][B(C₆F₅)₄]、[Pd(P(i-Pr)₃)₂(κ²-O，O’-O₂C-t-Bu)][B(C₆F₅)₄]、[(P(i-Pr)₃)₂Pd(κ²-O，O-O₂CCF₃)][B(C₆F₅)₄]、[(P(i-Pr)₃)₂Pd(κ²-O，O-O₂CC₆F₅)][B(C₆F₅)₄]、[(P(i-Pr)₃)₂Pd(κ²-O，O-O₂CC₆H₅)][B(C₆F₅)₄]、[(P(i-Pr)₃)₂Pd(κ²-O，O’-O₂CC₆H₄-p-(CF₃))][B(C₆F₅)₄]、[(P(i-Pr)₃)₂Pd(κ²-O，O-O₂CC₆H₄)-p-(OMe)][B(C₆F₅)₄]、[Pd(P(Cy)₂(CMe₃))₂(κ²-O，O’-O₂CCH₃)][B(C₆F₅)₄]、[Pd(P(Cy)(CMe₃)₂)₂(κ²-O，O’-O₂CCH₃)][B(C₆F₅)₄]、[Pd(P(i-Pr)₂(CMe₃))₂(κ²-O，O’-O₂CCH₃)][B(C₆F₅)₄]、[Pd(P(i-Pr)(CMe₃)₂)₂(κ²-O，O’-O₂CCH₃)][B(C₆F₅)₄]、[Pd(κ²-O，O’-OAc)(As(Cy)₃)₂][B(C₆F₅)₄]、[Pd(κ²-O，O’-OAc)(As(i-Pr)₃)₂][B(C₆F₅)₄]、[Pd(As-i-Pr₃)₂(O₂CCH₃)(NCCH₃)][B(C₆F₅)₄]、[Pd(As(Cy)₃)₂(O₂CCH₃)(NCCH₃)][B(C₆F₅)₄]、[(P(Cy-d₁₁)₃)₂Pd(NCMe)(O₂CCH₃)][B(C₆F₅)₄]、[(P(Cy-d₁)₃)₂Pd(NCMe)(O₂CCH₃)][B(C₆F₅)₄]、[Pd(O₂CCH₃)(P(Cy)₃)₂(MeCN)][B(C₆F₅)₄]、[Pd(O₂CCH₃)(P(i-Pr)₃)₂(MeCN)][B(C₆F₅)₄]、[Pd(O₂CCH₃)(P(i-Pr)₃)₂(MeCN)][B(C₆H₃-3，5-(CF₃)₂)₄]、[Pd(O₂CCH₃)(P(Cy)₃)₂(MeCN)][Al(OC(CF₃)₂C₆H₄CH₃)₄]、[Pd(O₂CCH₃)(P(i-Pr)₃)₂(MeCN)][Al(OC(CF₃)₂C₆H₄CH₃)₄]、[Pd(O₂C-t-Bu)](P(Cy)₃)₂(MeCN)[B(C₆F₅)₄]、[Pd(O₂CPh)(P(Cy)₃)₂(NCMe)][B(C₆F₅)₄]、[Pd(O₂CCF₃)(P(Cy)₃)₂(MeCN)][B(C₆F₅)₄]、[Pd(OAc)(P(Cy)₃)₂(NC₅H₅)][B(C₆F₅)₄]、[(P-i-Pr₃)₂Pd(O₂CCH₃)(NC₅H₅)][B(C₆F₅)₄]、[(P(Cy-d₁)₃)₂Pd(NCMe)(O₂CCH₃)][B(C₆F₅)₄]、[Pd(P(Cy)₃)₂(O₂CCH₃)(4-Me₂NC₅H₄N)][B(C₆F₅)₄]、[Pd(P(Cy)₃)₂(O₂CCH₃)(CNC₆H₃Me₂-2，6)][B(C₆F₅)₄]、trans-[(P-i-Pr₃)₂Pd(O₂CCH₃)(CNC₆H₃Me₂-2，6)][B(C₆F₅)₄]、[(PCy₂-t-Bu)₂Pd(O₂CCH₃)(MeCN)]B(C₆F₅)₄、[Pd(P(i-Pr)₂(CMe₃))₂(O₂CCH₃)(MeCN)][B(C₆F₅)₄]、[Pd(PCy₂-t-Bu)₂(O₂CCH₃)(MeCN)]B(C₆F₅)₄、cis-[Pd(P(i-Pr)₃)(κ²-p，C-P(i-Pr)₂(C(CH₃)₂)(NC₅H₅)][B(C₆F₅)₄]、cis-[Pd(P(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂)(2，6-Me₂py)][B(C₆F₅)₄]、cis-[Pd(P(i-Pr)₃)(κ²-p，C-P(i-Pr)₂(C(CH₃)₂)(2，6-Me₂pyz)][B(C₆F₅)₄]、cis-[Pd(P(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂))(4-t-BuC₅H₄N)][B(C₆F₅)₄]、[Pd(κ²-P，C-PCy₂(C₆H₁₀) (acetonitrile)][B(C₆F₅)₄]、[Pd(P(Cy)₃)(κ²-P，C-PCy₂(C₆H₁₀) - (pyrazine)][B(C₆F₅)₄]And [ PdP (Cy)]₃(κ²-P，C-PCy₂(C₆H₁₀) (pyridine)][B(C₆F₅)₄]。

47. The palladium compound of claim 1, wherein [ (E (R))₃)(E(R)₂R^*)Pd(LB)]_p[WCA]_rIs composed of

[Pd(P-(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂) (acetonitrile)][B(C₆F₅)₄]、

[Pd(P-(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂) (pyrazine)][B(C₆F₅)₄]、

[Pd(P-(i-Pr)₃)(κ²-P，C-P(i-Pr)₂(C(CH₃)₂) (pyridine)][B(C₆F₅)₄]。

48. The palladium compound of claim 1, wherein [ (E (R))₃)(E(R)₂R^*)Pd(LB)]_p[WCA]_rIs composed of

[Pd(κ²-P，C-PCy₂(C₆H₁₀) (acetonitrile)][B(C₆F₅)₄]、

[Pd(κ²-P，C-PCy₂(C₆H₁₀) - (pyrazine)][B(C₆F₅)₄]Or is

[Pd(κ²-P，C-PCy₂(C₆H₁₀) (pyridine)][B(C₆F₅)₄]。

49. The palladium compound of claim 1, wherein [ (E (R))₃)(E(R)₂R^*)Pd(LB)]_p[WCA]_rIs deuterated to be [ Pd (P (C)₃D₇)₃)(κ²-P，C-P(i-C₃D₇)₂(C(CD₃)₂) (acetonitrile)][B(C₆F₅)₄]Or

[Pd(P(C₆D₁₁)₃)(κ²-P，C-P(C₆D₁₁)₂(C₆D₁₀) (acetonitrile)][B(C₆F₅)₄]。

50. A method of forming a palladium pro-initiator complex comprising:

providing a palladium complex of the formula:

Pd(ER₃)_a(Q)_b

wherein E is an element of group 15 of the periodic Table of the elements, each R is independently hydrogen, deuterium, or a moiety containing an anionic hydrocarbyl group, Q is an anionic ligand, a is 1, 2, or 3, b is 1 or 2; and

a Weakly Coordinating Anion (WCA) salt is mixed with the palladium complex at a first temperature for a first period of time to react therewith.

51. The method of claim 50, wherein E is phosphorus, arsenic, antimony, or bismuth and Q is a carboxylate, thiocarboxylate, or dithiocarboxylate anion.

52. The method of claim 51, wherein E is phosphorus and Q is a carboxylate anion.

53. The method of claim 50 wherein said anionic hydrocarbyl containing moiety is linear and branched (C)₁-C₂₀) Alkyl, (C)₃-C₁₂) Cycloalkyl group, (C)₂-C₁₂) An alkenyl group,(C₃-C₁₂) Cycloalkenyl group, (C)₅-C₂₀) Polycyclic alkyl radical, (C)₅-C₂₀) Polycyclic alkenyl radical or (C)₆-C₁₂) And (4) an aryl group.

54. The method of claim 53, wherein the anionic hydrocarbyl containing moiety is isopropyl or cyclohexyl.

55. The method of claim 50, wherein E is phosphorus, Q is a carboxylate anion, and each R is cyclohexyl.

56. A method of forming a palladium pro-initiator complex comprising:

providing a palladium complex of the formula:

Pd(ER₃)_a(Q)₂

wherein E is an element of group 15 of the periodic Table of the elements, each R is independently hydrogen, deuterium, or a moiety containing an anionic hydrocarbyl group, Q is an anionic ligand, a is 1 or 2;

first reacting the palladium complex with an aromatic sulfonic acid at a first temperature for a first period of time, the sulfonic acid replacing one Q; and

the reacted palladium complex is then reacted with a Weakly Coordinating Anion (WCA) salt at a second temperature for a second period of time.

57. The method of claim 56, wherein E is phosphorus, arsenic, antimony, or bismuth and Q is a carboxylate, thiocarboxylate, or dithiocarboxylate anion.

58. The method of claim 57, wherein E is phosphorus and Q is a carboxylate anion.

59. The method of claim 56, wherein said anionic hydrocarbyl containing moiety is linear and branched (C)₁-C₂₀) Alkyl, (C)₃-C₁₂) Cycloalkyl group, (C)₂-C₁₂) Alkenyl, (C)₃-C₁₂) Cycloalkenyl group, (C)₅-C₂₀) Polycyclic alkyl radical, (C)₅-C₂₀) Polycyclic alkenyl radical or (C)₆-C₁₂) And (4) an aryl group.

60. The method of claim 59, wherein the anionic hydrocarbyl containing moiety is isopropyl or cyclohexyl.

61. The method of claim 56, wherein E is phosphorus, Q is a carboxylate anion, and each R is cyclohexyl.

62. A method for solution polymerization of norbornene-type monomers comprising:

providing a first solution comprising [ (E (R))₃)_aPd(Q)(LB)_b]_p[WCA]_rOr [ (E (R))₃)(E(R)₂R^*)Pd(LB)]_p[WCA]_rThe single-component palladium complex;

providing a second solution comprising one or more norbornene-type monomers dissolved in a second liquid support material;

mixing the first and second liquid carrier materials within a reaction vessel and heating the mixed liquid carrier materials within the reaction vessel to a first temperature for a period of time sufficient to cause polymerization of the one or more monomers in the presence of the palladium complex; and

after the period of time, the polymerized product is isolated.

63. A method for bulk polymerization of norbornene-type monomers comprising:

providing a carrier material comprising [ (E (R))₃)_aPd(Q)(LB)_b]_p[WCA]_rOr [ (E (R))₃)(E(R)₂R^*)Pd(LB)]_p[WCA]_rA solution of the single-component palladium complex shown;

providing one or more norbornene-type monomers;

adding said solution to said monomer to form a polymerizable mixture; and

heating the mixture to a first temperature for a time sufficient to cause polymerization of the one or more monomers in the presence of the palladium complex.

64. The palladium compound of claim 1, where E is phosphorus (P) or arsenic (As).

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