Energy polmerizable compositions containing organometallic initiators

We claim:

1. An energy polymerizable composition comprising a cationically polymerizable material selected from the group consisting of cyclic ethers, vinyl ethers, N-vinyl compounds, cyclic formals, and cyclic organosiloxanes, and a catalytically effective amount of an ionic salt of an organometallic complex cation and a halogen containing complex anion of a metal or metalloid, said ionic salt being capable of adding an intermediate strength nucleophile or upon photolysis capable of liberating at least one coordination site, the metal in said organometallic complex cation being selected from elements of Periodic Groups IV, VI, VIB, VIIB, and VIIIB, the total charge on said metal in said cation resulting in a net residual positive charge to said complex.

2. The composition according to claim 1 wherein said ionic salt has the formula: ##STR6## wherein M.sup.a, M.sup.b, M.sup.c, and M.sup.d each represents a metal selected from the elements of Periodic Groups IVB, VB, VIB, VIIB, and VIIIB;

with the proviso that Formula I can represent a mononuclear, binuclear, trinuclear, or tetranuclear complex compound comprising M.sup.a, M.sup.a M.sup.b, M.sup.a M.sup.b M.sup.c, or M.sup.a M.sup.b M.sup.c M.sup.d respectively with their attendent ligands, L;

L.sup.1a, L.sup.1b, L.sup.1c, and L.sup.1d each represents none, 1, 2, or 3 ligands contributing .pi.-electrons that can be the same or different ligands selected from substituted and unsubstituted acyclic and cyclic unsaturated compounds and groups and substituted and unsubstituted carbocyclic aromatic and heterocyclic aromatic compounds, each capable of contributing two to twelve .pi.-electrons to the valence shell of M.sup.a, M.sup.b, M.sup.c, and M.sup.d respectively;

L.sup.2a , L.sup.2b, L.sup.2c and L.sup.2d each represents none or 1 to 6 ligands contributing an even number of .sigma.-electrons that can be the same or different selected from mono-, di-, and tri-dentate ligands, each contributing 2, 4, or 6 .sigma.-electrons to the valence shell of M.sup.a, M.sup.b, M.sup.c, and M.sup.d respectively;

L.sup.3b, L.sup.3c, and L.sup.3d each represents none, 1 or 2 ligands contributing one .sigma.-electron each to the valence shell of M.sup.a, M.sup.b, M.sup.c, and M.sup.d respectively;

L.sup.4 represents none or 1 to 6 bridging ligands containing .pi.-electrons that can be the same or different ligand selected from substituted and unsubstituted acyclic and cyclic unsaturated compounds and groups and substituted and unsubstituted carbocyclic aromatic and heterocyclic aromatic compounds, each capable of acting as a bridging ligand contributing 2 to 24 .pi.-electrons to the valence shells of two or more metal atoms M.sup.a, M.sup.b, M.sup.c, or M.sup.d simultaneously;

L.sup.5 represents none or 1 to 12 bridging ligands contributing an even number of .sigma.-electrons that can be the same or different selected from mono, di, and tri-dentate ligands, each donating 2, 4, or 6 .sigma.-electrons to the valence shells of two or more metal atoms M.sup.a, M.sup.b, M.sup.c, or M.sup.d simultaneously;

L.sup.6 represents none or 1 to 12 bridging ligands contributing 1, 2, 3, or 4 .sigma.-electrons to the valence shells of two or more metal atoms M.sup.a, M.sup.b, M.sup.c, or M.sup.d simultaneously;

with the proviso that the total electronic charge contributed to M.sup.a, M.sup.b, M.sup.c, and M.sup.d by the ligands L.sup.1a, L.sup.2a, L.sup.3 a, L.sup.1b, L.sup.2b, .sup.3b, L.sup.1c, L.sup.2c, L.sup.3c, L.sup.1d, L.sup.2d, L.sup.3d, L.sup.4, L.sup.5, and L.sup.6 plus the sum of ionic charge on M.sup.a, M.sup.b, M.sup.c, and M.sup.d results in a residual net positive charge of e to the complex;

e is an integer having a value of 1, 2, or 3, the residual electrical charge of the complex cation;

X is a halogen containing complex anion of a metal or metalloid;

f is an integer of 1 to 3, the number of complex anions required to neutralize the charge e on the complex cation, and

g, h, j, and k independently are 0 or 1, with at least one of them being equal to 1.

3. The composition according to claim 2

wherein the ligands L.sup.1a, L.sup.1b, L.sup.1c, and L.sup.1d of the ionic salt each contains less than 100 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron;

the ligands L.sup.2a, L.sup.2b, L.sup.2c, and L.sup.2d of the ionic salt each is selected from:

a. monodentate ligands having up to 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, and

b. polydentate ligands capable of forming with metal M.sup.a, M.sup.b, M.sup.c, or M.sup.d a 4-, 5-, or 6-membered saturated or unsaturated ring containing up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, in addition to the metal atom;

the ligands L.sup.3 a, L.sup.3b, L.sup.3c, and L.sup.3d of the ionic salt each has up to 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron;

the bridging ligand L.sup.4 of the ionic salt contains less than 100 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen and nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron;

the bridging ligand L.sup.5 of the ionic salt contains up to 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, and boron; and

the bridging radical L.sup.6 of the ionic salt has up to 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron.

4. The composition according to claim 2 wherein the ligands L.sup.1a, L.sup.1b, L.sup.1c, and L.sup.1d each is independently unsubstituted or substituted by a group selected from hydrocarbyl, hydrocarbyloxy, hydrocarbylmercapto, hydrocarbyloxycarbonyl, hydrocarbylcarbonyl, hydrocarbylcarbonamido, phenyl, azo, boryl, halo, hydroxy, cyano, nitro, nitroso, oxo, dimethylamino, diphenylphosphino, trimethylsiloxy, and condensed rings, said group containing up to 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron.

5. The composition according to claim 2 wherein said L.sup.1a, L.sup.1b, L.sup.1c, L.sup.1d, L.sup.2a, L.sup.2b, L.sup.2c, L.sup.2d, l.sup.3a, L.sup.3b, L.sup.3c, L.sup.3d, L.sup.4, L.sup.5, and L.sup.6 ligands independently are groups on a polymeric chain.

6. The composition according to claim 1 wherein said ionic salt has the formula:

wherein

M.sup.m represents a metal selected from elements of the Periodic Groups IVB, VB, VIB, VIIB, and VIIIB;

L.sup.7 represents none, one, or two .pi.-electron contributing ligands that can be the same or different ligand selected from substituted and unsubstituted acyclic and alicyclic unsaturated compounds and groups and substituted and unsubstituted carbocyclic and heterocyclic aromatic compounds, each capable of contributing two to twelve .pi.-electrons to the valence shell of M.sup.m ;

L.sup.8 represents none or 1 to 6 ligands that can be the same or different ligand selected from mono-, di-, and tri-dentate ligands, each contributing 2, 4, or 6 .sigma.-electrons to the valence shell of M.sup.m ;

with the proviso that the total electronic charge contributed to M.sup.m by L.sup.7 and L.sup.8 plus the ionic charge on M.sup.m results in a residual net positive charge of e to the complex;

e is an integer having a value of 1, 2, or 3, the residual electrical charge of the complex cation;

X is a halogen containing complex anion of a metal or metalloid; and

f is an integer of 1 to 3, the number of complex anions required to neutralize the charge of e on the complex cation.

7. The composition according to claim 6

wherein ligand L.sup.7 of the ionic salt contains less than 100 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron;

ligand L.sup.8 of the ionic salt is selected from:

a. monodentate ligands having up to 30 carbon atoms and up to 2 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron, and

b. polydentate ligands capable of forming with metal M.sup.m a 4-, 5-, or 6-membered saturated or unsaturated ring containing up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron in addition to the metal atom.

8. The composition according to claim 7 wherein ligand L.sup.7 is substituted by a group selected from hydrocarbyl, hydrocarbyloxy, hydrocarbylmercapto, hydrocarbyloxycarbonyl, hydrocarbylcarbonyl, hydrocarbylcarbonamido, phenyl, azo, boryl, halo, hydroxy, cyano, nitro, nitroso, oxo, dimethylamino, diphenylphosphino, trimethylsiloxy, and condensed rings, said group containing up to 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron.

9. The composition according to claim 1 wherein said ionic salt has the formula:

wherein

M.sup.p represents a metal selected from Cr, Mo, W, Mn, Re, Fe, and Co;

L.sup.9 represents one or two .pi.-electron contributing ligands that can be the same or different ligand selected from substituted and unsubstituted .eta..sup.3 -allyl, .eta..sup.5 -cyclopentadienyl, and .eta..sup.7 -cycloheptatrienyl and .eta..sup.6 -aromatic compounds selected from .eta..sup.6 -benzene and substituted .eta..sup.6 -benzene compounds and compounds having 2 to 4 fused rings each capable of contributing 3 to 12 .pi.-electrons to the valence shell of M.sup.p ;

L.sup.10 represents none, 1 to 3 ligands contributing two .sigma.-electrons to the valence shell of M.sup.p ;

with the proviso that the total electronic charge contributed to M.sup.p by ligands L.sup.9 and L.sup.10, plus the ionic charge on M.sup.p results in a residual net positive charge of q to the complex;

q is an integer having a value of 1 or 2, the residual electrical charge of the complex cation;

Y is a halogen containing complex anion selected from AsF.sub.6 --, SbF.sub.6 --, and SbF.sub.50 H--, and

n is an integer of 1 or 2, the number of complex anions required to neutralize the charge q on the complex cation

10. The composition according to claim 9 wherein L.sup.9 is substituted by a group selected from hydrocarbyl, hydrocarbyloxy, hydrocarbylmercapto, hydrocarbyloxycarbonyl, hydrocarbylcarbonyl, hydrocarbylcarbonamido, phenyl, azo, boryl, halo, hydroxy, cyano, nitro, nitroso, oxo, dimethylamino, diphenylphosphino, trimethylsiloxy, and condensed rings, said group containing up to 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron.

11. The composition according to claim 9 wherein ligand L.sup.9 of the ionic salt contains up to 24 carbon and up to two heteroatoms selected from nitrogen, oxygen, and sulfur.

12. The composition according to claim 9 wherein ligand L.sup.10 of the ionic salt is selected from carbon monoxide and the nitrosonium ion.

13. The composition according to claim 1 wherein said salt is present in an amount in the range of 0.01 to 20 weight percent of said cationically polymerizable material.

14. The composition according to claim 1 wherein said salt is present in an amount in the range of 0.5 to 5.0 weight percent of said cationically polymerizable material.

15. The composition according to claim 1 wherein said salt is present in an amount in the range of 1.0 to 2.0 weight percent of said cationically polymerizable material.

16. The composition according to claim 1 further comprising in the range of 0.1 to 10 parts by weight of a spectral sensitizer per part of organometallic salt.

17. The composition according to claim 1 wherein said cyclic ether is an epoxy group-containing material.

18. The composition according to claim 17 which is a 1,2, 1,3-, or 1,4- cyclic ether.

19. The composition according to claim 1 wherein said cyclic ether is a 1,2-cyclic ether.

20. A process of polymerizing cationically polymerizable materials comprising the steps:

a. admixing a cationically polymerizable material selected from the group consisting of cyclic ethers, vinyl ethers, N-vinyl compounds, cyclic formals, cyclic organosiloxanes, with a cationically effective amount of an ionic salt of an organometallic complex, said ionic salt of an organometallic complex cation being capable of adding an intermediate strength nucleophile or upon photolysis capable of liberting at least one coordination site, said metal in said organometallic complex being selected from elements of Periodic Groups IVB, VB, VIB, VIIB, VIIIB, and

b. curing the resulting admixture with at least one of a thermal and actinic radiation source.

21. The process according to claim 20 wherein said curing step is accomplished by subjecting said composition to actinic radiation followed by heat.

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TECHNICAL FIELD

The present invention relates to a process for the polymerization of cationically-sensitive materials employing as polymerization initiator a certain class of ionic organometallic compounds. In another aspect, it relates to polymerizable compositions containing cationically-sensitive materials and organometallic complex compounds. In a further aspect, it relates to certain organometallic polymerization initiators.

BACKGROUND ART

The prior art describes various processes for the initiation of cationic polymerization, particularly the polymerization of epoxy materials. It is known to cure epoxy materials by use of curing additives such as polybasic anhydrides, organic peroxides, and quinone. It is further known that a metallocene, such as ferrocene, can be used as a curing accelerator for epoxy materials and is described in U.S. Pat. No. 3,705,129. U.S. Pat. Nos. 3,709,861 and 3,714,006 describe the use of cyclopentadienylmanganese tricarbonyl for the acceleration of the light-catalyzed reaction between polyepoxides and acid anhydrides or polymercaptans. U.S. Pat. No. 3,867,354 discloses the use of bis- and tris-salicylic acid complexes of chromium(III) to catalyze the reaction between epoxides and carboxylic acids, and U.S. Pat. No. 4,237,242 relates to the use of transition metal complexes (chromium, manganese, iron, etc.) of acetylacetonate type ligands to accelerate the thermally initiated reaction of carboxylic acid group-containing polymers with polyepoxides. Each of the above-mentioned patents teaches the acceleration of the reaction between polyepoxides and polyfunctional curing additives, but they do not teach the polymerization of epoxide group-containing compositions not containing a curing additive.

The polymerization of cationically-polymerizable materials, specifically epoxide group-containing materials, in the absence of curing additives is, however, well known. Among such processes are those in which the polymerization catalyst (also called sensitizer or initiator) is (1) a radiation-sensitive onium salt of a Lewis acid (e.g. diazonium salts as is described in U.S. Pat. No. 3,794,576 and U.S. Pat. No. 4,080,274; halonium salts as is disclosed in U.S. Pat. No. 4,026,705; and the onium salts of Group VIA elements, particularly the sulfonium salts, as are disclosed in U.S. Pat. No. 4,058,400); (2) a dicarbonyl chelate compound of a Group IIIA--VA element as is disclosed in U.S. Pat. No. 4,086,091; (3) a silver salt which is used for the polymerization of tetrahydrofuran as is described by Woodhouse, et al., J. Am. Chem. Soc. 100, 996 (1978); and (4) titanocene dichloride which is used for the polymerization of epichlorohydrin and 2-chloroethylvinyl ether as is described by Kaerijama et al., J. Polym. Sci., Chem. Ed. 10, 2833 (1972) and Ibid, 14, 1547 (1976). Compositions containing the above-mentioned catalysts are unsatisfactory because without the addition of optical sensitizers they are limited to ultraviolet radiation for polymerization. Furthermore, the dicarbonyl chelates are moisture sensitive and the titanocene dichloride requires a co-catalyst.

DISCLOSURE OF THE INVENTION

The present invention provides a process for the polymerization of cationically-sensitive materials utilizing as catalyst a cationic compound which is a salt of an organometallic complex cation. By selection of the metal and ligands in the organometallic complex and the counterion used, the relative thermal stability and wavelength of sensitivity (from 200 to 600 nm) can be adapted for various applications.

In accordance with the present invention there is provided energy-curable compositions comprising: p1 a) a cationically-polymerizable material and

b) a catalytically-effective amount of an ionic salt of an organometallic complex cation sufficient to effect polymerization, said ionic salt of an organometallic complex cation being capable of adding an intermediate strength nucleophile such as triphenylphosphine or upon photolysis capable of liberating at least one coordination site, said metal of said organometallic complex cation being selected from elements of Periodic Groups IVB, VB, VIB, VIIB, and VIIIB.

There is also provided a process for the polymerization of cationically sensitive material comprising the steps of:

a) mixing the cationically-sensitive material with a catalytically-effective amount of the ionic salt of an organometallic complex cation, thereby forming a mixture, and

b) allowing the mixture to polymerize or adding energy to the mixture to effect polymerization thereof.

As used in this application:

"catalytically effective amount" means a quantity sufficient to effect polymerization of the cationically-polymerizable material at least to a degree to increase the viscosity of the composition, and

"intermediate strength nucleophile" means a nucleophile intermediate in strength between hydride and chloride, e.g., trialkyl- and triarylphosphines, trialkyl- and triarylphosphites, pyridines, and anilines.

DETAILED DESCRIPTION OF THE INVENTION

The ionic salts of the organometallic complex cations useful in the compositions and processes of the invention are compounds having the formula: ##STR1## wherein M.sup.a, M.sup.b, M.sup.c, and M.sup.d represent metal atoms which may be the same or different selected from the elements of Periodic Groups IVB, VB, VIB, VIIB, and VIIIB;

with the proviso that Formula I can represent a mononuclear, binuclear, trinuclear, or tetranuclear complex compound comprising M.sup.a, M.sup.a M.sup.b, M.sup.a M.sup.b M.sup.c, or M.sup.a M.sup.b M.sup.c M.sup.d respectively with their attendent ligands, L;

each L.sup.1a, L.sup.1b, L.sup.1c, and L.sup.1d represents none, or 1, 2, or 3 ligands contributing .pi.-electrons that can be the same or different ligand selected from substituted and unsubstituted acyclic and cyclic unsaturated compounds and groups and substituted and unsubstituted carbocyclic aromatic and heterocyclic aromatic compounds, each capable of contributing two to twelve .pi.-electrons to the valence shell of M.sup.a, M.sup.b, M.sup.c, and M.sup.d, respectively;

each L.sup.2a, L.sup.2b, L.sup.2c, and L.sup.2 d represents none, or 1 to 6 ligands contributing an even number of .sigma.-electrons that can be the same or different selected from mono-, di-, and tri-dentate ligands, each donating 2, 4, or 6 .sigma.-electrons to the valence shell of M.sup.a, M.sup.b, M.sup.c, and M.sup.d, respectively;

each L.sup.3a, L.sup.3b, L.sup.3c, and L.sup.3d represents none, 1, or 2 ligands contributing one .sigma.-electron each to the valence shell of M.sup.a, M.sup.b, M.sup.c, and M.sup.d, respectively;

L.sup.4 represents none, or 1 to 6 bridging ligands containing .sigma.-electrons that can be the same or different ligand selected from substituted and unsubstituted acyclic and cyclic unsaturated compounds and groups and substituted and unsubstituted carbocyclic aromatic and heterocyclic aromatic compounds, each capable of acting as a bridging ligand contributing 2 to 24 .pi.-electrons to the valence shells of two or more metal atoms M.sup.a, M.sup.b, M.sup.c, or M.sup.d simultaneously;

L.sup.5 represents none, or 1 to 12 bridging ligands contributing an even number of .sigma.-electrons that can be the same or different selected from mono-, di-, and tri-dentate ligands, each donating 2, 4, or 6 .sigma.-electrons to the valence shells of two or more metal atoms M.sup.a, M.sup.b, M.sup.c, or M.sup.d simultaneously;

L.sup.6 represents none or 1 to 12 bridging ligands contributing 1, 2, 3, or 4 .sigma.-electrons to the valence shells of two or more metal atoms M.sup.a, M.sup.b, M.sup.c, or M.sup.d simultaneously; with the proviso that the total electronic charge contributed to M.sup.a, M.sup.b, M.sup.c, and M.sup.d by the ligands L.sup.1a, L.sup.2a, L.sup.3a, L.sup.1b, L.sup.2b, L.sup.3b, L.sup.1c, L.sup.2c, L.sup.3c, L.sup.1d, L.sup.2 d, L.sup.3d L.sup.4, L.sup.5, and L.sup.6 plus the sum of ionic charge on M.sup.a, M.sup.b, M.sup.c, and M.sup.d results in a residual net positive charge of e to the complex;

e is an integer having a value of 1, 2, or 3, the residual electrical charge of the complex cation;

X is a halogen-containing complex anion of a metal or metalloid;

f is an integer of 1 to 3, the number of complex anions required to neutralize the charge e on the complex cation; and

g, h, j, and k independently are 0 or 1, with at least one of them being equal to 1.

By Periodic Group IVB is meant the elements Ti, Zr, and Hf.

By Periodic Group VB is meant the elements V, Nb, and Ta.

By Periodic Group VIB is meant the elements Cr, Mo, and W.

By Periodic Group VIIB is meant the elements Mn, Tc, and Re, and

By periodic Group VIIIB is meant the elements Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt.

In a preferred composition of the invention, the salts of the organometallic cation have the formula:

wherein

M.sup.m represents a metal selected from elements of the Periodic Groups IVB, VB, VIB, VIIB, and VIIIB;

L.sup.7 represents none, one or two ligands contributing .pi.-electrons that can be the same or different ligand selected from the same group of ligands from which L.sup.1a, L.sup.1b, L.sup.1c, and L.sup.1d ligands of Formula I is selected;

L.sup.8 represents none or 1 to 6 ligands contributing an even number of .sigma.-electrons that can be the same or different ligand selected from the same group of ligands from which L.sup.2a, L.sup.2b, L.sup.2c, and L.sup.2 d ligands of Formula I is selected;

with the proviso that the total electronic charge contributed to M.sup.m by L.sup.7 and L.sup.8 plus the ionic charge on M.sup.m results in a residual net positive charge of e to the complex; and e, f, and X have the same definition as given in Formula I.

In a most preferred composition of the invention, the salts of the organometallic cation are novel and have the formula:

wherein

M.sup.p represents a metal selected from Cr, Mo, W, Mn, Re, Fe, and Co;

L.sup.9 represents 1 or 2 ligands contributing .pi.-electrons that can be the same or different ligand selected from substituted and unsubstituted .eta..sup.3 -allyl, .eta..sup.5 -cyclopentadienyl, and .eta..sup.7 -cycloheptatrienyl and .eta..sup.6 -aromatic compounds selected from .eta..sup.6 -benzene and substituted .eta..sup.6 -benzene compounds and compounds having 2 to 4 fused rings each capable of contributing 3 to 8 .pi.-electrons to the valence shell of M.sup.p ;

L.sup.10 represents none or 1 to 3 ligands contributing an even number of .sigma.-electrons that can be the same or different ligand selected from carbon monoxide or nitrosonium;

with the proviso that the total electronic charge contributed to M.sup.p by L.sup.9 and L.sup.10 plus the ionic charge on metal M.sup.p results in a net residual positive charge of q to the complex, and

q is an integer having a value of 1 or 2, the residual electrical charge of the complex cation;

Y is a halogen-containing complex anion selected from AsF.sub.6.sup.-, SbF.sub.6.sup.- and SbF.sub.5 OH.sup.- ; and

n is an integer having a value of 1 or 2, the numbers of complex anions required to neutralize the charge q on the complex cation.

Salts of organometallic cations having Formulas I, II, and III are radiation sensitive in addition to being thermally sensitive.

All ligands L.sup.1a to L.sup.10 are well known in the art of transition metal organometallic compounds.

Ligands L.sup.1a, L.sup.1b, L.sup.1c, and L.sup.1d in Formula I, and L.sup.7 in Formula II, are provided by any monomeric or polymeric compound having an accessible unsaturated group, i.e., an ethylenic ##STR2## group; acetylenic, --C.tbd.C-- group; or aromatic group which have accessible .pi.-electrons regardless of the total molecular weight of the compound. By "accessible", it is meant that the compound (or precursor compound from which the accessible compound is prepared) bearing the unsaturated group is soluble in a reaction medium, such as an alcohol, e.g., methanol; a ketone, e.g., methyl ethyl ketone; an ester, e.g., amyl acetate; a halocarbon, e.g., trichloroethylene; an alkane, e.g., decalin; an aromatic hydrocarbon, e.g., anisole; an ether, e.g., tetrahydrofuran; etc, or that the compound is divisible into very fine particles of high surface area so that the unsaturated group (including aromatic group) is sufficiently close to a metal atom to form a .pi.-bond joining the unsaturated group to the metal atom. By polymeric compound, it is meant, as explained below, that the ligand can be a group on a polymeric chain.

Illustrative of ligands L.sup.1a, L.sup.1b, L.sup.1c, L.sup.1d, and L.sup.7 are the linear and cyclic olefinic and acetylenic compounds having less than 100 carbon atoms, preferably having less than 60 carbon atoms, and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, boron, antimony, tellurium, silicon, germanium, and tin, such as, for example, ethylene, acetylene, propylene, methylacetylene, 1-butene, 2-butene, diacetylene, butadiene, 1,2-dimethylacetylene, cyclobutene, pentene, cyclopentene, hexene, cyclohexene, 1,3-cyclohexadiene, cyclopentadiene, 1,4-cyclohexadiene, cycloheptene, 1-octene, 4-octene, 3,4-dimethyl-3-hexene, and 1-decene; .eta..sup.3 -allyl, .eta.3-pentenyl, norbornadiene, .eta.5-cyclohexadienyl, .eta.6-cycloheptatriene, .eta..sup.8 -cyclooctatetracene, and substituted and unsubstituted carbocyclic and heterocyclic aromatic ligands having up to 25 rings and up to 100 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, boron, antimony, tellurium, silicon, germanium, and tin, such as, for example, .eta.5-cyclopentadienyl, .eta..sup.6 -benzene, .eta..sup.6 -mesitylene, .eta..sup.6 -hexamethylbenzene, .eta.6-fluorene, .eta..sup.6 -naphthalene, .eta..sup.6 -anthracene, .eta..sup.6 -chrysene, .eta..sup.6 -pyrene, .eta.7-cycloheptatrienyl, .eta..sup.6 -triphenylmethane, .eta..sup.12 -paracyclophane, .eta.12-1,4-diphenylbutane, .eta..sup.5 -pyrrole, .eta..sup.5 -thiophene, .eta..sup.5 -furan, .eta..sup.6 -pyridine, .eta.6-97 -picoline, .eta.6-quinaldine, .eta..sup.6 -benzopyran, .eta..sup.6 -thiochrome, .eta..sup.6 -benzoxazine, .eta..sup.6 -indole, .eta..sup.6 -acridine, .eta..sup.6 -carbazole, .eta..sup.6 -triphenylene, .eta..sup.6 -silabenzene, .eta.6-arsabenzene, .eta..sup.6 -stibabenzene, .eta..sup.6 -2,4,6-triphenylphosphabenzene, .eta.5-selenophene, .eta..sup.6 -dibenzostannepine, .eta..sup.5 -tellurophene, .eta..sup.6 -phenothiarsine, .eta..sup.6 -selenanthrene, .eta..sup.6 -phenoxaphosphine, .eta..sup.6 -phenarsazine, .eta..sup.6 -phenatellurazine, and .eta..sup.6 -1-phenylborabenzene. Other suitable aromatic compounds can be found by consulting any of many chemical handbooks.

As mentioned before, the ligand can be a unit of a polymer, for example the phenyl group in polystyrene, poly(styrene-cobutadiene), poly(styrene-comethyl methacrylate), poly(.alpha.-methylstyrene), polyvinylcarbazole, and polymethylphenylsiloxane; the cyclopentadiene group in poly(vinylcyclopentadiene), poly(.eta..sup.4 -cyclopentadiene); the pyridine group in poly(vinylpyridine), etc. Polymers having a weight average molecular weight up to 1,000,000 or more can be used. It is preferable that 5 to 50 percent of the unsaturated or aromatic groups present in the polymer be complexed with metallic cations.

Each of the ligands L.sup.1a, L.sup.1b, L.sup.1c, L.sup.1d, and L.sup.7 can be substituted by groups that do not interfere with the complexing of the ligand with the metal atom or which do not reduce the solubility of the ligand to the extent that complexing with the metal atom does not take place. Examples of substituting groups, all of which preferably have less than 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron, include hydrocarbyl groups such as methyl, ethyl, butyl, dodecyl, tetracosanyl, phenyl, benzyl, allyl, benzylidene, ethenyl, and ethynyl; hydrocarbyloxy groups such as methoxy, butoxy, and phenoxy; hydrocarbylmercapto groups such as methylmercapto (thiomethoxy), phenylmercapto (thiophenoxy); hydrocarbyloxycarbonyl such as methoxycarbonyl and phenoxycarbonyl; hydrocarbylcarbonyl such as formyl, acetyl, and benzoyl; hydrocarbylcarbonyloxy such as acetoxy, benzoxy, and cyclohexanecarbonyloxy; hydrocarbylcarbonamido, e.g., acetamido, benzamido; azo; boryl; halo, e.g., chloro, iodo, bromo, and fluoro; hydroxy; cyano; nitro; nitroso, oxo; dimethylamino; diphenylphosphino, diphenylarsino; diphenylstibine; trimethylgermane; tributyltin; methylseleno; ethyltelluro; and trimethylsiloxy; condensed rings such as benzo, cyclopenta; naphtho, indeno; and the like.

Ligands L.sup.2a, L.sup.2b, L.sup.2c, and L.sup.2d in Formula I, and L.sup.8 in Formula II are provided by monodentate and polydentate compounds preferably containing up to about 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, and tellurium, in addition to the metal atom, following loss of zero, one, or two hydrogens, the polydentate compounds preferably forming with the metal, M.sup.a, M.sup.b, M.sup.c, M.sup.d, and M.sup.m, a 4-, 5-, or 6-membered saturated or unsaturated ring. Examples of suitable monodentate compounds or groups are carbon monoxide, carbon sulfide, carbon selenide, carbon telluride, alcohols such as ethanol, butanol, and phenol; nitrosonium (i.e., NO.sup.+); compounds of Group VA elements such as ammonia, phosphine, trimethylamine, trimethylphosphine, triphenylamine, triphenylphosphine, triphenylarsine, triphenylstibine, tributylphosphite, isonitriles such as phenylisonitrile, butylisonitrile; carbene groups such as ethoxymethylcarbene, dithiomethoxycarbene; alkylidenes such as methylidene, ethylidene; suitable polydentate compounds or groups include 1,2-bis(diphenylphosphino)ethane, 1,2-bis(diphenylarsino)ethane, bis(diphenylphosphino)methane, ethylenediamine, propylenediamine, diethylenetriamine, 1,3-diisocyanatopropane, and hydridotripyrazolylborate; the hydroxycarboxylic acids such as glycollic acid, lactic acid, salicylic acid; polyhydric phenols such as catechol and 2,2'-dihydroxybiphenyl; hydroxyamines such as ethanolamine, propanolamine, and 2-aminophenol; dithiocarbamates such as diethyldithiocarbamate, dibenzyldithiocarbamate; xanthates such as ethyl xanthate, phenyl xanthate; the dithiolenes such as bis(perfluoromethyl)-1,2-dithiolene; aminocarboxylic acids such as alanine, glycine and o-aminobenzoic acid; dicarboxylic diamides such as oxalamide, biuret; diketones such as 2,4-pentanedione; hydroxyketones such as 2-hydroxyacetophenone; .alpha.-hydroxyoximes such as salicyladoxime; ketoximes such as benzil oxime; and glyoximes such as dimethylglyoxime. Other suitable groups are the inorganic groups such as, for example, CN.sup.-, SCN.sup.-, F.sup.-, OH.sup.-, Cl.sup.-, Br.sup.-, I.sup.-, and H.sup.- and the organic groups such as, for example, acetoxy, formyloxy, benzoyloxy, etc. As mentioned before, the ligand can be a unit of a polymer, for example the amino group in poly(ethyleneamine); the phosphino group in poly(4-vinylphenyldiphenylphosphine); the carboxylic acid group in poly(acrylic acid); and the isonitrile group in poly(4-vinylphenylisonitrile).

Suitable radicals L.sup.3a, L.sup.3b, L.sup.3c, and L.sup.3d in Formula I include any group having in its structure an atom with an unshared electron. Suitable groups can contain any number of carbon atoms and hetero atoms but preferably contain less than 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron. Examples of such groups are hydrocarbyl groups such as methyl, ethyl, propyl, hexyl, dodecyl, phenyl, tolyl, etc.; unsaturated hydrocarbyl groups such as vinyl, allyl, butenyl, cyclohexenyl; the hydrocarbyl derivatives of a Group IVA element such as trimethylgermanium, triphenyltin, and trimethylsilyl, etc.; and organic groups such as formyl, acetyl, propionyl, acryloyl, octadecoyl, benzoyl, toluenesulfonyl, oxalyl, malonyl, o-phthaloyl.

Ligand L.sup.4 in Formula I is provided by any monomeric or polymeric compound having an accessible unsaturated group, such as an acetylenic, --C.tbd.C-- group or an aromatic group which have accessible .pi.-electrons regardless of the total molecular weight of the compound.

Illustrative of ligand L.sup.4 are the linear and cyclic diene and acetylenic compounds preferably having less than 60 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, boron, antimony, tellurium, silicon, germanium, and tin, such as for example, acetylene, methylacetylene, diacetylene, butadiene, 1,2-dimethylacetylene, 1,3-cyclohexadiene, cyclopentadiene, and 1,4-cyclohexadiene; .eta..sup.3 -allyl, .eta..sup.3 -pentenyl, norbornadiene, .eta..sup.5 -cyclohexadienyl, .eta..sup.6 -cycloheptatriene, .eta..sup.8 -cyclooctatetracene, and substituted and unsubstituted carbocyclic and heterocyclic aromatic ligands having up to 25 rings and up to 100 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, boron, antimony, tellurium, silicon, germanium, and tin, such as, for example, .eta..sup.5 -cyclopentadienyl, .eta..sup.6 -benzene, .eta..sup.6 -mesitylene, .eta..sup.6 -hexamethylbenzene, .eta..sup.6 -fluorene, .eta..sup.6 -naphthalene, .eta..sup.6 -anthracene, .eta..sup.6 -chrysene, .eta..sup.6 -pyrene, .eta..sup.7 -cycloheptatrienyl, .eta..sup.6 -triphenylmethane, .eta.5-pyrrole, .eta..sup.5 -thiophene, .eta..sup.5 -furan, .eta..sup.6 -pyridine, .eta..sup.6 -Y-picoline, .eta..sup.6 -quinaldine, .eta..sup.6 -benzopyran, .eta..sup.6 -thiochrome, .eta..sup.6 -benzoxazine, .eta..sup.6 -indole, .eta..sup.6 -acridine, .eta..sup.6 -carbazole, .eta..sup.6 -(1,2,3,4,4a,12a)-.eta.6-(7,8,9,10,10a,10b)chrysene, .eta..sup.6 -triphenylene, .eta..sup.6,.eta.6'-paracyclophane, 06,06'-1,4-diphenylbutane, .eta..sup.6 -silabenzene, .eta..sup.6 -arsabenzene, .eta..sup.6 -stibabenzene, .eta..sup.6 -2,4,6-triphenylphosphabenzene, .eta..sup.5 -selenophene, .eta..sup.6 -dibenzostannepine, .eta..sup.5 -tellurophene, .eta..sup.6 -phenothiarsine, .eta..sup.6 -selenanthrene, .eta..sup.6 -phenoxaphosphine, .eta.6-phenarsazine, .eta. .sup.6 -phenatellurazine, and .eta..sup.6 -1-phenylborabenzene. Other suitable aromatic compounds can be found by consulting any of many chemical handbooks.

Each of the ligands L.sup.4 can be substituted by groups that do not interfere with the complexing of the ligand with the metal atom or which do not reduce the solubility of the ligand to the extent that complexing with the metal atom does not take place. Examples of substituting groups, all of which preferably have less than 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, tellurium, silicon, germanium, tin, and boron, include hydrocarbyl groups such as methyl, ethyl, butyl, dodecyl, tetracosanyl, phenyl, benzyl, allyl, benzylidene, ethenyl, and ethynyl; hydrocarbyloxy groups such as methoxy, butoxy, and phenoxy; hydrocarbylmercapto groups such as methylmercapto (thiomethoxy), phenylmercapto (thiophenoxy); hydrocarbyloxycarbonyl such as methoxycarbonyl and phenoxycarbonyl; hydrocarbylcarbonyl such as formyl, acetyl, and benzoyl; hydrocarbylcarbonyloxy such as acetoxy, benzoxy, and cyclohexanecarbonyloxy; hydrocarbylcarbonamido, e.g., acetamido, benzamido; azo; boryl; halo, e.g., chloro, iodo, bromo, and fluoro, hydroxy; cyano; nitro; nitroso, oxo; dimethylamino; diphenylphosphino, diphenylarsino; diphenylstibine; trimethylgermane; tributyltin; methylseleno; ethyltelluro; and trimethylsiloxy; condensed rings such as benzo, cyclopenta; naphtho, indeno; and the like.

Ligand L.sup.5 is provided by monodentate and polydentate compounds preferably containing up to about 30 carbon atoms and up to 10 hetero atoms selected from nitrogen, sulfur, oxygen, phosphorus, arsenic, selenium, antimony, and tellurium. Examples of suitable monodentate compounds or groups are carbon monoxide, carbon sulfide, carbon selenide carbon telluride, alcohols such as ethanol, butanol, and phenol; nitrosonium (i.e., NO.sup.+); compounds of Group VA elements such as triphenylamine, triphenylphosphine, triphenylarsine, triphenylstibine, isonitriles such as phenylisonitrile; suitable polydentate compounds or groups include 1,2-bis(diphenylphosphino)ethane, 1,2-bis-(diphenylarsino)ethane, bis(diphenylphosphino)methane, ethylenediamine, propylenediamine, diethylenetriamine, 1,3-diisocyanatopropane, and hydridotripyrazolylborate; the hydroxycarboxylic acids such as glycollic acid, lactic acid, salicylic acid; polyhydric phenols such as catechol and 2,2'-dihydroxybiphenyl; hydroxyamines such as ethanolamine, propanolamine, and 2-aminophenol; dithiocarbamates such as diethyldithiocarbamate, dibenzyldithiocarbamate; xanthates such as ethyl xanthate, phenyl xanthate; the dithiolenes such as bis(perfluoromethyl)