Reactivity of phosphido-bridged heteronuclear compounds: insertion of carbon monoxide and diphenylacetylene into the phosphido bridge of RuCo(CO)7(.mu.-PPh2). X-ray structure of RuCo(CO)5(.mu.-CO)[.mu.-.eta.2-PPh2C(O)C(Ph)C(Ph)]

Abstract

The crystal structure analyses of 6 and 11 were performed by Dr. F. J. Hollander, U.C. Berkeley X-ray Crystallographic Facility, and that of 8 by Dr. W. Tótsch and J. Bularzik, K. Kourtakis, and J. Nitschke, at the same location. We thank Professor . B. Abrahamson, University of Oklahoma for a preprint. M.T. is the recipient of a Royal Fellowship of Norway. K.P.C.V. was a Camille and Henry Dreyfus Teacher-Scholar (1978-1983

Formation of complexes with C ⋯ H ⋯ Mn interactions from reactions of dienes or acetylene with a µ-hydrido heterometallic dimer; X-ray crystal structures of [(η5-C5H5)MoMn(µ-H)(µ-PPh2)(CO)6], [(η5-C5H5)MoMn{µ–σ : η3-CH2C(Me)CHMe}(µ-PPh2)(CO)4], and [(η5-C5H5)MoMn{µ–σ : η4-CHCHCH2CHPPh2}(CO)4]

“…spectrum (4) is tentatively formulated as an allyl complex, in which the ligand is +bonded to the molybdenum atom. Complex (4) is converted slowly into (2b) in solution at room temperature under N2 and is presumably an intermediate in the formation of this latter complex. Under CO (1 atm, room temp.…”

Stepwise oxidative cleavage of bis(diphenylphosphino)methane in the substituted ruthenium clusters Ru3(CO)8(.mu.-.eta.2-Ph2PCH2PPh2)2 and Ru4(.mu.-H)4(CO)10(.mu.-.eta.2-Ph2PCH2PPh2)

“…C. Thermolysis of Ru3(#t-H)(CO)7(Ai3-i)4-(C6H6)PCHP-(C6H6)(C6H4))(µ-2-) (3). Compound 3 (50 mg) was dissolved in toluene (25 mL), and the solution was heated under reflux.…”

“…Reaction of 3(µ-)(00)7(µ3-4-(€6 5) € -(06 5)(06 4))(µ-» 2-) (3) with H2. Compound 3 (50 mg) was dissolved in toluene (25 mL).…”

Reactions of the heteronuclear alkyne-bridged cobalt–molybdenum complex [(OC)3Co{µ-C2(CO2Me)2}Mo(CO)2(η5-C5H5)] with PPh2H, P2Ph4and PPh2(SPh)

“…The 31P-{1H) NMR spectrum displays a singlet at 6 64.0 consistent with a p-PPh, bridge. In the 13C-{ 'H} NMR spectrum at 293 K the three CO groups give rise to three separate resonances, the most downfield being a doublet with a coupling constant of 15 Hz, at a chemical shift characteristic of a molybdenum-bound -The thermolysis of the bis-substituted secondary phosphine complex 5 at 338 K in toluene gives, in addition to unreacted starting material, the complex [(q 5-C . _ H ,)(OC)Mo { p-C( CO, Me)=CH( C0,Me)) (p-PPh,)Co(CO)(PPh,H)] 10 in 59% yield.…”