Synthesis and chemistry of heterobimetallic fulvalene complexes containing W, Mo, and Rh Academic Article uri icon

abstract

  • The photo- and thermal chemistry of the heterobimetallic fulvalene (Fv) complex Fv[W(CO) 3 Me][Rh(CO) 2 ] (1) was investigated, and compounds Fv(CO) 2 MeWRh(CO)[μ-CO] (2), Fv(CO) 3 WRh(CO)Me (3), and Fv(CO) 3 WRh(CO)C(O)Me (4) were characterized. Reaction mechanisms were studied by labeling experiments using 13 CO and by analogy to the MoRh system. The complexes Fv(CO) 3 MoRh(CO)C(O) Me (7) and Fv(CO) 3 MoRh(CO)Me (8) were characterized. Reaction of 3 and 4 with PMe 3 gave the zwitterionic species Fv[W (CO) 3 ][Rh(PMe 3 ) 2 Me] (16) and Fv[W(CO) 3 ][Rh(PMe 3 ) 2 C(O)Me] (17), respectively. An excess of PMe 3 , led to the mononuclear compounds FvRh(PMe 3 ) 2 Me (18) and FvRh(PMe 3 ) 2 C(O)Me (19). The latter was reacted with Mo(CO) 3 (EtCN) 3 to give zwitterionic Fv[Mo(CO) 3 ]Rh(PMe 3 ) 2 C(O)Me] (20). The X-ray structures of the acyl complexes 4 and 17 were obtained. X-ray data of 4: P1, a = 13.529(3) Å, b = 15.813(3) Å, c = 16.164(3) Å, α = 62.72(1)°, β = 87.24(1)°, gg = 86.32(1)°, V = 3065.9(11) Å 3 , Z = 8, R w = 0.045. X-ray data of 17: P2 1 /n, a = 15.412(4) Å, b = 9.745(2) Å, c = 18.209(6) Å, α = 90.0°, β = 93.46(2)°, γ = 90.0°, V = 2730.0(22) Å 3 , Z = 4, R w = 0.0303. © 1994.

author list (cited authors)

  • Kahn, A. P., Boese, R., Blümel, J., & Vollhardt, K.

citation count

  • 9

publication date

  • June 1994