Polymer-supported phosphorus ligands for catalysis Number:7,098,261 from the United States Patent and Trademark Office (PTO) owispatent Novel phosphine and phosphine oxide ligands are prepared using polymeric supports. These compounds can be easily cleaved from the support, and along with the corresponding supported compounds, used as ligands in the preparation of novel, metal-complexed catalysts.<H phosphorus, catalysis, Polymer, support, 7098261.html, Patent, pto, 7098261

Title: Polymer-supported phosphorus ligands for catalysis

Abstract: Novel phosphine and phosphine oxide ligands are prepared using polymeric supports. These compounds can be easily cleaved from the support, and along with the corresponding supported compounds, used as ligands in the preparation of novel, metal-complexed catalysts.

Patent Number: 7,098,261 Issued on 08/29/2006 to Fagan, et al.

Inventors: Fagan; Paul J. (Wilmington, DE), Li; George Yanwu (Wilmington, DE)
Assignee: E. I. du Pont de Nemours and Company (Wilmington, DE)

Appl. No.: 10/187,706

Filed: July 1, 2002

Current U.S. Class: 524/110 ; 435/7.1; 436/518; 525/255

Current International Class: C08K 5/15 (20060101)

Field of Search: 524/110 436/518 525/255 435/7.1

References Cited [Referenced By]

U.S. Patent Documents


5650456	July 1997	Yun et al.

Primary Examiner: Richter; Johann
Assistant Examiner: Nwaonicha; Chukwuma

Claims

We claim:

1. A process to prepare coumarin comprising contacting salicylaldehyde with an acrylate of the formula ##STR00070## wherein R.sub.10 is an alkyl group of 1 6 carbons.

2. The process of claim 1 wherein the process is performed in the presence of a catalytic amount of a coordination compound comprising one or more transition metals complexed to a ligand selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7 ##STR00071## wherein: SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1 12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R.sub.1, R.sub.2 and R.sub.3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ.sub.1, OQ.sub.2, PQ.sub.3Q.sub.4, and NQ.sub.5Q.sub.6, where Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.5, and Q.sub.6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R.sub.2 and R.sub.3 together, R.sub.1 and R.sub.3 together, or R.sub.1 and R.sub.2 together can optionally form a ring.

3. The process of claim 2 wherein SS is selected from the group consisting of polyolefins, polyacrylates, polymethacrylates, and copolymers thereof, and wherein the transition metal is selected from Periodic Group VIII.

Description

FIELD OF INVENTION

This invention relates to the preparation of novel polymer-supported phosphine and phosphine oxide compounds and the corresponding free compounds after cleavage from support. These compounds are useful as ligands in the preparation of metal-containing catalysts.

BACKGROUND

As is generally known in prior art, chelating phosphine compounds when bound to metal atoms are useful as catalysts. To facilitate separation of the catalysts from a chemical process, phosphorus ligands have been attached to solid supports such as polymers ("Supported Metal Complexes", D. Reidel Publishing, 1985; Acta. Polymer. 1996,47, 1; "Chem. Met.-Carbon Bond", Hartley, F. R (Ed), 1987, vol. 4, pp. 1163 1225; Neckers, J. Macromol. Sci., Chem. 1987, A24, 431 48). Interest in using the combinatorial "split and mix synthesis" approach to generate polymer-bound ligands which could be tested as catalysts has brought to fore the importance of new chemistry with which to attach phosphine ligands to polymer supports (Balkenhohl et al., Angew. Chem., Int. Ed. Engl. 1996, 35, 2288 2337; Gilbertson et al., J. Organometallics 1996, 15, 4678 4680; Gilbertson et al., J. Am. Chem. Soc. 1994, 116, 4481 4482).

Novel processes have been discovered to prepare new compositions of matter that contain chelating phosphine compounds, including compounds of asymmetric diphosphines. Phosphine compounds have been shown to be useful when combined with transition metals as catalysts for chemical processes. The processes can also be utilized in a combinatorial scheme to produce libraries of phosphine compounds.

Addition of aldehyde in salicylaldehydes to acetylenes is known, but is unknown for addition to alkenes. (Kokai Tokkyo Koho JP 7853632; JP 76128205 Kokubo et al., J. Org. Chem. 1997, 62, 4564 4565.) The new phosphorus compounds have been shown to be useful as ligands in catalysts for the decarbonylation of the salicylaldehyde and insertion of the alkene, followed by ring closure forming a coumarin.

SUMMARY OF THE INVENTION

This invention is directed to compositions and processes to prepare polymer supported phosphine and phosphine oxide compounds and the corresponding free compounds after their cleavage from the polymer support.

More specifically, the invention is directed to a process to prepare a supported phosphine compound selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7

##STR00001## wherein:

SS is a solid support; A is a divalent group of 1 12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ.sub.1, OQ.sub.2, PQ.sub.3Q.sub.4, and NQ.sub.5Q.sub.6, where Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.5, and Q.sub.6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R.sub.2 and R.sub.3 together, R.sub.1 and R.sub.3 together, or R.sub.1 and R.sub.2 together can optionally form a ring, the process comprising the steps of: a) contacting (i) a phosphine selected from the group consisting of XPR.sub.1R.sub.2, XR.sub.3P-A-PR.sub.1R.sub.2, HP(.dbd.O)R.sub.1R.sub.2, HP(.dbd.O) R.sub.3-A-PR.sub.1R.sub.2, and HP(.dbd.O)R.sub.3-A-P(.dbd.O)R.sub.1R.sub.2 wherein X is a halogen, with (ii) the solid support, resulting in at least one P in the phosphine attached indirectly or directly to the solid support via one or more covalent bonds, and b) optionally replacing one or more substituent of the group R.sub.1, R.sub.2, or R.sub.3 with any other substituent of the group R.sub.1, R.sub.2, or R.sub.3.

In all process and compositions embodiments of the invention, the preferred SS is selected from the group consisting of polyolefins, polyacrylates, polymethacrylates, and copolymers thereof.

The process is useful in producing the preferred supported phosphine compounds selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A.

##STR00002## wherein:

Z is a divalent attaching group covalently attached to at least one P in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, --O--, --S--, and --NR.sub.4--, where R.sub.4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and

L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

More particularly, this process to prepare supported phosphine compounds uses the supported phosphine compound of Formula 1A, where the process comprises the steps of: a) contacting (i) at least 2 molar equivalents of a phosphine of the Formula XR.sub.3P-A-PR.sub.1R.sub.2 wherein X is a halogen, with (ii) no more than one molar equivalent of Z, resulting in one P in the phosphine being covalently bonded to the Z, and b) optionally replacing one or more substitutent of the group R.sub.1, R.sub.2, and R.sub.3 with any one or more of R.sub.1, R.sub.2, and R.sub.3. In this process the SS is more preferably polystyrene; L is --CH.sub.2--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the process may use a supported phosphine compound of Formula 2A, with the process comprising the steps of: a) contacting (i) a phosphine of the Formula PR.sub.1R.sub.2X wherein X is a halogen, with (ii) the solid support, resulting in one P in the phosphine being covalently bonded to Z, and b) optionally replacing one or both of R.sub.1 and R.sub.2 with any other R.sub.1 or R.sub.2. In this process the SS is more preferably polystyrene; is --CH.sub.2--; Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R.sub.1 and R.sub.2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aromatic or alkyl ring.

Alternatively, this process may use the supported phosphine compound of Formula 3A, with the process comprising the steps of: a) contacting (i) no more than one molar equivalent of a phosphine of the Formula XR.sub.3P-A-PR.sub.1R.sub.2 wherein X is a halogen, with (ii) at least two molar equivalents of Z, resulting in both of the P in the phosphine being covalently bonded to the Z; and b) optionally replacing one or more of R.sub.1 and R.sub.2 with any one or more of R.sub.1 and R.sub.2. In this process the SS is more preferably polystyrene; L is --CH.sub.2--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R.sub.1 and R.sub.2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, this process may use the supported phosphine compound of Formula 4A, with the process comprising the steps of: a) contacting (i) a phosphine of the Formula HP(.dbd.O) R.sub.3-A-PR.sub.1R.sub.2 with (ii) the solid support, resulting in one P in the phosphine being covalently bonded to Z; and b) optionally replacing one or more of R.sub.1, R.sub.2, and R.sub.3 with any one or more of R.sub.1, R.sub.2, and R.sub.3. In this process the SS is more preferably polystyrene; L is --CH.sub.2--; Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, this process may use the supported phosphine compound of Formula 5A with the process comprising the steps of: a) contacting (i) a phosphine of the Formula HP(.dbd.O)R.sub.1R.sub.2 with (ii) a solid support of the formula

##STR00003## wherein the P in the solid support is covalently bonded to Z and Z' is selected from the group consisting of alkenyls, resulting in the P in the phosphine being covalently bonded to the P in the solid support via Z'; and b) optionally replacing one or more of R.sub.1, R.sub.2, and R.sub.3 with any one or more of R.sub.1, R.sub.2, and R.sub.3. In this process the SS more preferably is polystyrene; L is --CH.sub.2--; Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

This invention is also directed to a process to prepare a combinatorial library of supported phosphine compounds selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7

##STR00004## wherein:

SS is a solid support;

A is a divalent group of 1 12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups;

R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ.sub.1, OQ.sub.2, PQ.sub.3Q.sub.4, and NQ.sub.5Q.sub.6, where Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.5, and Q.sub.6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and

R.sub.2 and R.sub.3 together, R.sub.1 and R.sub.3 together, or R.sub.1 and R.sub.2 together can optionally form a ring, the process comprising the steps of: a) contacting (i) one or more phosphines selected from the group consisting of XPR.sub.1R.sub.2, XR.sub.3P-A-PR.sub.1R.sub.2, HP(.dbd.O)R.sub.1R.sub.2, HP(.dbd.O) R.sub.3-A-PR.sub.1R.sub.2, and HP(.dbd.O)R.sub.3-A-P(.dbd.O)R.sub.1R.sub.2 wherein X is a halogen, with (ii) one or more solid supports, resulting in at least one P in each phosphine attached indirectly or directly to the solid support via one or more covalent bonds, and b) optionally replacing one or more R.sub.1, R.sub.2, or R.sub.3 with any other R.sub.1, R.sub.2, or R.sub.3.

The process is useful in producing a combinatorial library in which the preferred supported phosphine compounds are selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A

##STR00005## wherein:

Z is a divalent attaching group covalently attached to at least one P in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, --O--, --S--, and --NR.sub.4--, where R.sub.4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

More preferably, this process to prepare a combinatorial library of supported phosphine compounds uses Formula 1A with the process comprising the steps of: a) contacting at least 2 molar equivalents of one or more phosphines of the Formula XR.sub.3P-A-PR.sub.1R.sub.2 wherein X is a halogen, with no more than one molar equivalent of one or more of Z, resulting in one P in each phosphine being covalently bonded to the Z; and b) optionally replacing one or more of R.sub.1, R.sub.2, and R.sub.3 with any one or more of R.sub.1, R.sub.2, and R.sub.3. In this process the SS more preferably is polystyrene; L is --CH.sub.2--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the process may use the supported phosphine compounds of Formula 2A with the process comprising the steps of: a) contacting one or more phosphines of the Formula PR.sub.1R.sub.2X wherein X is a halogen, with one or more solid supports, resulting in one P in each phosphine being covalently bonded to Z; and b) optionally replacing one or both of R.sub.1 and R.sub.2 with any other R.sub.1 or R.sub.2. In this process the SS more preferably is polystyrene; L is --CH.sub.2--; Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R.sub.1 and R.sub.2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aromatic, or alkyl ring.

Alternatively, the process may use the supported phosphine compounds of Formula 3A with the process comprising the steps of: a) contacting no more than one molar equivalent of one or more phosphines of the Formula XR.sub.3P-A-PR.sub.1R.sub.2 wherein X is a halogen, with at least two molar equivalents of one or more of Z, resulting in both of the P in each phosphine being covalently bonded to the Z; and b) optionally replacing one or more of R.sub.1 and R.sub.2 with any one or more of R.sub.1 and R.sub.2. In this process SS is more preferably polystyrene; L is --CH.sub.2--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R.sub.1 and R.sub.2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl or alkyl ring.

Alternatively, the process may use the supported phosphine compounds of Formula 4A with the process comprising the steps of: a) contacting one or more phosphines of the Formula HP(.dbd.O)R.sub.3-A-PR.sub.1R.sub.2 with one or more solid supports, resulting in one P in each phosphine being covalently bonded to Z; and b) optionally replacing one or more of R.sub.1, R.sub.2, and R.sub.3 with any one or more of R.sub.1, R.sub.2, and R.sub.3. In this process the SS is more preferably polystyrene; L is --CH.sub.2--; Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the process may use the supported phosphine compounds of Formula 5A with the process comprising the steps of: a) contacting one or more phosphines of the Formula HP(.dbd.O)R.sub.1R.sub.2 with one or more solid supports of the formula

##STR00006## wherein the P in the solid support is covalently bonded to Z and Z' is selected from the group consisting of alkenyls, resulting in the phosphorus in each phosphine being covalently bonded to the phosphorus in the solid support via Z', and b) optionally replacing one or more of R.sub.1, R.sub.2, and R.sub.3 with any one or more of R.sub.1, R.sub.2, and R.sub.3. In this process the SS is more preferably polystyrene; L is --CH.sub.2--; Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

Additionally, the invention is directed at a process to prepare a phosphine compounds of Formulae 8, 9, 10, 1 1, and 12

##STR00007## wherein:

A is a divalent group of 1 12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups;

R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ.sub.1, OQ.sub.2, PQ.sub.3Q.sub.4, and NQ.sub.5Q.sub.6, where Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.5, and Q.sub.6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle;

any of R.sub.5, R.sub.6, R.sub.7, and R.sub.8 can optionally together with any other of R.sub.5, R.sub.6, R.sub.7, and R.sub.8 form a ring;

the process comprising the steps of: a) contacting (i) a supported phosphine selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7

##STR00008## wherein:

SS is a solid support wherein at least one P in the phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1 12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometal groups; R.sub.1, R.sub.2 and R.sub.3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ.sub.1, OQ.sub.2, PQ.sub.3Q.sub.4, and NQ.sub.5Q.sub.6, where Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.5, and Q.sub.6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R.sub.2 and R.sub.3 together, R.sub.1 and R.sub.3 together, or R.sub.1 and R.sub.2 together can optionally form a ring with (ii) a compound of the Formula ER.sub.9, wherein E is an electrophilic group and Rg is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ.sub.1, OQ.sub.2, PQ.sub.3Q.sub.4, and NQ.sub.5Q.sub.6, where Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.5, and Q.sub.6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; thereby forming the corresponding compound of Formulae 1, 2, 3, 4, 5, 6, and 7; and b) optionally replacing one or more substituent of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8 with any other substituent of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8.

More preferably, the process for preparing a phosphine compound uses a supported phosphine selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A

##STR00009## wherein:

Z is a divalent attaching group covalently attached to at least one P in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, --O--, --S--, and --NR.sub.4--, where R.sub.4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms; A is an optionally-substituted carbon chain of 1 3 carbon atoms; R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy; and any of R.sub.5, R.sub.6, R.sub.7, and R.sub.8 can optionally together with any other of R.sub.5, R.sub.6, R.sub.7, and R.sub.8 form a ring. Still more preferably in this process E is selected from the group consisting of hydrogen, PCl.sub.2, and SiMe.sub.3, and R.sub.5 is a halogen.

Also in this process, the supported phosphine compound is selected from the group consisting of Formulae 1 and 3, and the phosphine compound is of Formula 8. Also in this process at least one substitutent of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8 differs from the other substitutent of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8.

Also in this process, Z is preferably selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is preferably selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.5, R.sub.6, R.sub.7,and R.sub.8 are preferably independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are preferably independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8 can optionally together with any other substituent of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8 form a ring.

Alternatively, the process may use the supported phosphine compound of Formula 2 and the phosphine compound of Formula 9. In this process more preferably Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.5, R.sub.6, and R.sub.7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R.sub.5, R.sub.6, and R.sub.7 can optionally together with any other substituent of the group R.sub.5, R.sub.6, and R.sub.7 form a ring.

Alternatively, the process may use the supported phosphine compound of Formula 4 and the phosphine compound of Formula 10. In this process more preferably Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.5, R.sub.6, and R.sub.7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R.sub.5, R.sub.6, and R.sub.7 can optionally together with any other substituent of the group R.sub.5, R.sub.6, and R.sub.7 form a ring.

Alternatively, the process may use the supported phosphine compound selected from the group consisting of Formulae 3 and 5, and the phosphine compound of Formula 11. In this process more preferably Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.6, R.sub.7, and R.sub.8 are independently selected from the group consisting of Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R.sub.6, R.sub.7, and R.sub.8 can optionally together with any other substituent of the group R.sub.6, R.sub.7, and R.sub.8 form a ring.

Alternatively, the process may use the supported phosphine compound of Formula 2 and the phosphine compound of Formula 12. I this process more preferably Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.5 and R.sub.6 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R.sub.5 and R.sub.6 can optionally together with any other substituent of the group R.sub.5 and R.sub.6 form a ring.

This invention is still further directed to a process to prepare a combinatorial library of phosphine compounds selected from the group consisting of Formulae 8, 9, 10, 11, and 12

##STR00010## wherein:

A is a divalent group of 1 12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy; and any of R.sub.5, R.sub.6, R.sub.7, and R.sub.8 can optionally together with any other of R.sub.5, R.sub.6, R.sub.7, and R.sub.8 form a ring;

the process comprising the steps of: a) contacting (i) one or more supported phosphines selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7

##STR00011## wherein:

SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1 12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ.sub.1, OQ.sub.2, PQ.sub.3Q.sub.4, and NQ.sub.5Q.sub.6, where Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.5, and Q.sub.6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R.sub.2 and R.sub.3 together, R.sub.1 and R.sub.3 together, or R.sub.1 and R.sub.2 together can optionally form a ring with (ii) one or more compounds of the Formula ER.sub.9, wherein E is an electrophilic group and R.sub.9 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ.sub.1, OQ.sub.2, PQ.sub.3Q.sub.4, and NQ.sub.5Q.sub.6, where Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.5, and Q.sub.6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; thereby forming the corresponding compounds of Formulae 1, 2, 3, 4, 5, 6, and 7; and b) optionally replacing one or more substitutents of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8 with any other substitutent of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8.

More particularly the process may use the supported phosphine compounds of the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A

##STR00012## wherein:

Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, --O--, --S--, and --NR.sub.4--, where R.sub.4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms; A is an optionally-substituted carbon chain of 1 3 carbon atoms; R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy; and any of R.sub.5, R.sub.6, R.sub.7, and R.sub.8 can optionally together with any other of R.sub.5, R.sub.6, R.sub.7, and R.sub.8 form a ring.

In this process preferably E is selected from the group consisting of hydrogen, PCl.sub.2, and SiMe.sub.3, and R.sub.5 is a halogen. Additionally in this process preferably the supported phosphine compounds are selected from the group consisting of Formulae 1 and 3, and the phosphine compound is Formula 8. More preferaably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R.sub.5, R.sub.6, R.sub.7, and R.sub.8 can optionally together with any other of R.sub.5, R.sub.6, R.sub.7, and R.sub.8 form a ring.

Alternatively in this process the preferred supported phosphine compounds are of Formula 2, and the phosphine compounds are of Formula 9. More preferably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.5, R.sub.6, and R.sub.7, are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R.sub.5, R.sub.6, and R.sub.7 can optionally together with any other of R.sub.5, R.sub.6, and R.sub.7 form a ring.

Alternatively in this process the preferred supported phosphine compounds are of Formula 4 and the phosphine compounds are of Formula 10. More preferably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.5, R.sub.6, and R.sub.7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R.sub.5, R.sub.6, and R.sub.7 can optionally together with any other of R.sub.5, R.sub.6, and R.sub.7 form a ring.

Alternatively in this process the preferred supported phosphine compounds are selected from the group consisting of Formulae 3 and 5, and the phosphine compounds are of Formula 11. More preferably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.6, R.sub.7, and R.sub.8 are independently selected from the group consisting of Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R.sub.6, R.sub.7, and R.sub.8 can optionally together with any other of R.sub.6, R.sub.7, and R.sub.8 form a ring.

Alternatively in this process the preferred supported phosphine compounds are of Formula 2, and the phosphine compounds are of Formula 12. More preferably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.5 and R.sub.6 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R.sub.5 and R.sub.6 can optionally together with any other of R.sub.5 and R.sub.6 form a ring.

This invention is still further directed to a supported phosphine compound selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7

##STR00013## wherein:

SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1 12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ.sub.1, OQ.sub.2, PQ.sub.3Q.sub.4, and NQ.sub.5Q.sub.6, where Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.5, and Q.sub.6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R.sub.2 and R.sub.3 together, R.sub.1 and R.sub.3 together, or R.sub.1 and R.sub.2 together can optionally form a ring.

More preferably the supported phosphine compound is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A

##STR00014## wherein:

Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, --O--, --S--, and --(NR.sub.4)--, where R.sub.4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

Alternatively, the preferred supported phosphine compound is Formula 1A. More preferably in this supported phosphine compound the SS is polystyrene; L is --CH.sub.2--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the preferred supported phosphine compound is Formula 2A. More preferably in this supported phosphine compound the SS is polystyrene; L is --CH.sub.2--; Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R.sub.1 and R.sub.2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aromatic, or alkyl ring.

Alternatively, the preferred supported phosphine compound is Formula 3A. More preferably in this supported phosphine compound the SS is polystyrene; L is --CH.sub.2--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R.sub.1 and R.sub.2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the preferred supported phosphine compound is Formula 4A. More preferably in the supported phosphine compound of claim 63 the SS is polystyrene; L is --CH.sub.2--; Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the preferred supported phosphine compound is Formula 5A. More preferably in this supported phosphine compound the SS is polystyrene; L is --CH.sub.2--; Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

This invention is still further directed to a combinatorial library of supported phosphine compounds selected from the group consisting of Formulae 1,2, 3,4,5,6, and 7

##STR00015## wherein:

SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1 12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ.sub.1, OQ.sub.2, PQ.sub.3Q.sub.4, and NQ.sub.5Q.sub.6, where Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.5, and Q.sub.6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R.sub.2 and R.sub.3 together, R.sub.1 and R.sub.3 together, or R.sub.1 and R.sub.2 together can optionally form a ring.

Preferably the combinatorial library of this invention uses the supported phosphine compounds selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A

##STR00016## wherein:

Z is a divalent attaching group covalently attached to at least one phosphorus in each phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, --O--, --S--, and --(NR.sub.4)--, where R.sub.4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

Preferably, the combinatorial library uses the supported phosphine compounds of Formula 1A. More preferably in this combinatorial the SS is polystyrene; L is --CH.sub.2--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the combinatorial library uses the supported phosphine compounds of Formula 2A. More preferably in this combinatorial the SS is polystyrene; L is --CH.sub.2--; Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R.sub.1 and R.sub.2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aromatic, or alkyl ring.

Alternatively, the combinatorial library uses the supported phosphine compounds of Formula 3A. More preferably in this combinatorial library the SS is polystyrene; L is --CH.sub.2--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R.sub.1 and R.sub.2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.30, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the combinatorial library uses the supported phosphine compounds of Formula 4A. More preferably in this combinatorial library the SS is polystyrene; L is --CH.sub.2--; Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the combinatorial library uses the supported phosphine compounds of Formula 5A. more preferably in this combinatorial library the SS is polystyrene; L is --CH.sub.2--; Z is selected from the group consisting of optionally-substituted carbon chain of 1 10 carbon atoms, --(NR.sub.4)--, and --O--; A is selected from the group consisting of an optionally-substituted carbon chain of 1 3 carbon atoms and an optionally-substituted carbon ring of 6 12 carbon atoms; R.sub.4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where R.sub.1 and R.sub.2 together with the P form a phosphole, aryl, or alkyl ring.

The invention is still further directed to a combinatorial library of phosphine compounds selected from the group consisting of Formulae 8, 9, 10, 11, and 12

##STR00017## wherein:

A is a divalent group of 1 12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ.sub.1, OQ.sub.2, PQ.sub.3Q.sub.4, and NQ.sub.5Q.sub.6, where Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.5, and Q.sub.6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ.sub.1, OQ.sub.2, PQ.sub.3Q.sub.4, and NQ.sub.5Q.sub.6, where Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.5, and Q.sub.6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8 can optionally together with any other substituent of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8 form a ring.

Preferably in this combinatorial library of phosphine compounds A is an optionally-substituted carbon chain of 1 3 carbon atoms; R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R.sub.5, R.sub.6, R.sub.7, and R.sub.8 can optionally together with any other of R.sub.5, R.sub.6, R.sub.7, and R.sub.8 form a ring.

Preferably in this combinatorial library the phosphine compounds are of Formula 8. More preferably in this combinatorial library at least one of the substitutents of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8 differs from the other substituents of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8.

Alternatively in this combinatorial library of phosphine compounds A is an optionally-substituted carbon chain of 1 3 carbon atoms; R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8 can optionally together with any other substituent of the group R.sub.5, R.sub.6, R.sub.7, and R.sub.8 form a ring.

Preferably in this combinatorial library the phosphine compounds are of Formula 9. More preferably in this combinatorial library A is an optionally-substituted carbon chain of 1 3 carbon atoms; R.sub.5, R.sub.6, and R.sub.7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R.sub.5, R.sub.6, and R.sub.7 can optionally together with any other substituent of the group R.sub.5, R.sub.6, and R.sub.7 form a ring.

Preferably in this combinatorial library the phosphine compounds are of Formula 10. More preferably in this combinatorial library A is an optionally-substituted carbon chain of 1 3 carbon atoms; R.sub.5, R.sub.6, and R.sub.7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R.sub.5, R.sub.6, and R.sub.7 can optionally together with any other substituent of the group R.sub.5, R.sub.6, and R.sub.7 form a ring.

Preferably in this combinatorial library the phosphine compounds are of Formula 11. More preferably in this combinatorial library A is an optionally-substituted carbon chain of 1 3 carbon atoms; R.sub.6, R.sub.7, and R.sub.8 are independently selected from the group consisting of Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R.sub.6, R.sub.7, and R.sub.8 can optionally together with any other substituent of the group R.sub.6, R.sub.7, and R.sub.8 form a ring.

Preferably in this combinatorial library the phosphine compounds are of Formula 12. More preferably in this combinatorial library A is an optionally-substituted carbon chain of 1 3 carbon atoms; R.sub.5 and R.sub.6 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ.sub.1, OQ.sub.2, and PQ.sub.3Q.sub.4, where Q.sub.1, Q.sub.2, Q.sub.3, and Q.sub.4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R.sub.5 and R.sub.6 can optionally together with any other of R.sub.5 and R.sub.6 form a ring.

This invention is still further directed to a coordination compound comprising one or more transition metals complexed to a ligand selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7

##STR00018## wherein:

SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1 12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometal groups; R.sub.1, R.sub.2, and R.sub.3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ.sub.1, OQ.sub.2, PQ.sub.3Q.sub.4, and NQ.sub.5Q.sub.6, where Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.5, and Q.sub.6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R.sub.2 and R.sub.3 together, R.sub.1 and R.sub.3 together, or R.sub.1 and R.sub.2 together can optionally form a ring.

Preferably the transition metal is selected from Periodic Group VIII.

Preferably the coordination compound is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, SA, 6A, and 7A

##STR00019## wherein:

Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, --O--, --S--, and --(NR.sub.4)--, where R.sub.4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z an