Cleavage of phosphorus–phenyl and phosphorus-2-pyridyl bonds in the reactions of mixed phenyl-(2-pyridyl) phosphines with [Ru3(CO)12]

The compound [Ru3(CO)12] reacts at room temperature in tetrahydrofuran with tri(2-pyridyl)phosphine, P(2-C5H4N)3′ when catalysed by [N(PPh3)2]Cl, to give a product derived by cleavage of a phosphorus-2-pyridyl bond, [Ru3(µ-2-C5H4N){µ3-P(2-C5H4N)2}(CO)9]1. No simple substitution compounds could be isolated. The likely intermediates [Ru3(CO)n{P(2-C5H4N)3}](n= 10 and/or 11) spontaneously decarbonylate while a 2-pyridyl group migrates from phosphorus to ruthenium atoms. A similar reaction using phenyldi(2-pyridyl) phosphine, PPh(2-C5H4N)2′ leads to the competitive transfer of 2-pyridyl and pheyl groups to give almost equal quantities of two products, [Ru3(µ-2-C5H4N){µ3-PPh(2-C5H4N)}-(CO)9] and [Ru3(µ-PhCO){µ3-P(2-C5H4N)2}(CO)9]. The crystal structure of 1 shows that the 2-pyridyl group that has migrated bridges two ruthenium atoms with no Ru-Ru bond between them and that the di(2-pyridyl) phosphido ligand is triply bridging with one nitrogen co-ordinated and one free. As in the reported reaction of [Ru3(CO)12] with PPh2(2-C5H4N) to give [Ru3(µ-PhCO){µ3-PPh(2-C5H4N)}(CO)9], the reason why P-C bond cleavage occurs under remarkably mild conditions and the mechanism of the processes have still to be determined.

[1]  J. Bonnet,et al.  Structural characterization of 1,1,1,2,2,2,3,3,3‐nonacarbonyl‐1,2‐μ‐iodo‐1,2,3‐[μ3‐(phenylpyridylphosphido)‐μ‐P,N]‐triangulo‐triruthenium , 1992 .

[2]  M. Lanfranchi,et al.  Steric effects of the 2-(diphenylphosphino)pyridine bridging ligand in the synthesis of binuclear rhodium-palladium complexes. Crystal structures of [(CN-tert-Bu)2Cl2Rh(.mu.-Ph2PPy)Pd(.mu.-Cl)]2 and [(C8H12)Rh(.mu.-Cl)(.mu.-Ph2PPy)PdCl2] , 1991 .

[3]  G. Bruno,et al.  Rhodium-palladium and rhodium-platinum heterobinuclear complexes containing the 2-(diphenylphosphino)pyridine short-bite bridging ligand. X-ray crystal structure of [(.eta.5-C5H5)(CNBut)Rh(.mu.-Ph2PPy)Pd(CNBut)Cl]PF6 , 1991 .

[4]  D. Neibecker,et al.  Evidence for the lability of a bridging phosphido ligand under hydrogen atmosphere. Reactions of the cluster complex Ru3(.mu.3-P(C6H5)(C5H4N))(.mu.-P(C6H5)2)(CO)8 , 1988 .

[5]  F. Ahmed,et al.  Synthesis of the Co2(NO)3+ metallic core stabilized by two bridging aminophosphines, with BPh4− as a denitrosylating reagent , 1987 .

[6]  J. Bonnet,et al.  Cluster-promoted cleavage of a phosphorus-carbon bond under ambient conditions. Synthesis, structure, and stereospecific substitution reactions of the acyl cluster complex Ru3[.mu.-.eta.2-C(O)(C6H5)][.mu.3-.eta.2-P(C6H5)(C5H4N)](CO)9 , 1987 .

[7]  P. Bates,et al.  Intermediates in the conversion of [Os3(CO)11(PRPh2)](R = Me or Ph) into [Os3(µ3-C6H4)(µ3–PR)(CO)9]: crystal and molecular structures of [Os3-(µ-H)(µ3-C6H4PMePh-o)(CO)9] and [Os3(µ3-C6H4PMe-o)(CO)10] , 1987 .

[8]  Ruji J. Wang,et al.  Studies on binuclear complexes. , 1986 .

[9]  J. Bonnet,et al.  Unusual route to an acyl complex in cluster chemistry: synthesis, structure, and reactivity of Ru3(.mu.-.eta.2-C(O)(C6H5)(.mu.3-.eta.2-P(C6H5)(C5H4N)(CO)9 , 1986 .

[10]  F. Cotton,et al.  Reactivity of 2-(diphenylphosphino)pyridine toward complexes containing the quadruply bonded dirhenium(6+) ion core: ortho metalation and redox chemistry , 1984 .

[11]  A. Balch,et al.  Linking molybdenum or tungsten with platinum. The synthesis and molecular structure of PtMo(.mu.-Ph2Ppy)2(.mu.-CO)(CO)2Cl2 [Ph2Ppy = 2-(diphenylphosphino)pyridine] , 1983 .

[12]  A. Balch,et al.  Formation and reactivity of some heterobinuclear rhodium/platinum complexes with 2-(diphenylphosphino)pyridine as a bridging ligand , 1983 .

[13]  A. Balch,et al.  Preparation of binuclear complexes using 2-(diphenylphosphino)pyridine as a bridging ligand. Synthesis of some ruthenium complexes and their interaction with palladium complexes , 1982 .

[14]  L. Smart,et al.  New mode of ‘benzyne’ co-ordination. Crystal and molecular structure of Os3(CO)9(PEt)(C6H4) , 1980 .

[15]  G. Wilkinson,et al.  Tris(2-pyridyl)phosphine complexes of ruthenium(II) and rhodium(I). Hydroformylation of hex-1-ene by rhodium complexes , 1980 .