Two generalizable routes to terminal carbido complexes.
Desulfurization of the thiocarbonyl ligand in square pyramidal [Ru(CS)Cl2(PCy3)2] (1-S) via sulfur atom abstraction using [Mo(H)(eta2-Me2CNAr)(N[i-Pr]Ar)2] forms [Ru(C)Cl2(PCy3)2] (1) cleanly over several hours in benzene; isolated yield is 55%. Complex 1 is also formed in 87% isolated yield upon reaction of [Ru(CHR)(PCy3)2Cl2] (R = p-C6H4Me, 2; Ph, 3) with vinyl acetate in dichloromethane. Complex 1-S is re-formed quantitatively from 1 upon treatment with elemental sulfur in CH2Cl2, but is prepared most conveniently by treatment of crude [Ru(CS)Cl2(PPh3)2(OH2)] with excess PCy3 in toluene. Nearly quantitative conversion of 1 to [Ru(CO)Cl2(PCy3)2] (1-O) occurs upon addition of dimethyldioxirane solution in acetone to 1 dissolved in CH2Cl2 at ca. -90 degrees C.
Caskey
Stephen R
SR
Department of Chemistry, University of Michigan, Ann Arbor, 48109-1055, USA.
Stewart
Michael H
MH
Kivela
Jonathon E
JE
Sootsman
Joseph R
JR
Johnson
Marc J A
MJ
Kampf
Jeff W
JW