TY - JOUR

T1 - REACTIONS OF GACP* WITH A HEMILABILE DERIVATIVE OF RH 6(CO)16 - SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF TWO NOVEL HETEROMETALLIC CLUSTERS: RH6(CO)13- (ΜΚ3-PH2PC2H3)

AU - Grachova, E.V.

AU - Linti, G.

AU - Stammler, H.-G.

AU - Neumann, B.

AU - Tunik, S.P.

AU - Wadepohl, H.

PY - 2007

Y1 - 2007

N2 - The reaction of Rh6(CO)14(Ph2PCH=CH 2) with a twofold excess of GaCp* (Cp* = C 5Me5) affords two novel heterometallic clusters Rh 6(CO)13(μ,κ3-Ph2PC 2H3)(μ3-GaCp*) (1) and Rh 6(CO)13(κ1-Ph2PC 2H3)(μ3-GaCp*)2 (2) in a moderate yield. The hemilabile behavior of coordinated diphenylvinylphosphane in the starting cluster allows the easy insertion of GaCp* into the cluster coordination sphere, which eventually gives the cluster 1 with face-bridging coordination of the gallium fragment and the phosphane ligand recoordinated in an edge-bridging position. The further substitution of the vinyl function in 1 for the second GaCp* ligand affords cluster 2, where recoordination of the double bond is blocked by steric hindrance from adjacent GaCp* fragments. Both clusters were structurally characterized by X-ray crystallography in the solid state and by IR and NMR spectroscopy in solution. Hemilability of diphenylvinylphosphane in 1 was independently confirmed by the cluster reaction with CO, which gives the Rh6(CO)14(κ1-

AB - The reaction of Rh6(CO)14(Ph2PCH=CH 2) with a twofold excess of GaCp* (Cp* = C 5Me5) affords two novel heterometallic clusters Rh 6(CO)13(μ,κ3-Ph2PC 2H3)(μ3-GaCp*) (1) and Rh 6(CO)13(κ1-Ph2PC 2H3)(μ3-GaCp*)2 (2) in a moderate yield. The hemilabile behavior of coordinated diphenylvinylphosphane in the starting cluster allows the easy insertion of GaCp* into the cluster coordination sphere, which eventually gives the cluster 1 with face-bridging coordination of the gallium fragment and the phosphane ligand recoordinated in an edge-bridging position. The further substitution of the vinyl function in 1 for the second GaCp* ligand affords cluster 2, where recoordination of the double bond is blocked by steric hindrance from adjacent GaCp* fragments. Both clusters were structurally characterized by X-ray crystallography in the solid state and by IR and NMR spectroscopy in solution. Hemilability of diphenylvinylphosphane in 1 was independently confirmed by the cluster reaction with CO, which gives the Rh6(CO)14(κ1-

M3 - Article

SP - 140

EP - 146

JO - Berichte der deutschen chemischen Gesellschaft

JF - Berichte der deutschen chemischen Gesellschaft

SN - 0365-9496

IS - 1

ER -