Reactions of Dianionic Carbonylmetalates with Heteroallenes: Reduction of Carbonylsulfide, Thioisocyanates, Isocyanates and Carbodiimides by Group 6 and 8 Carbonylmetalates

摘要

Dianionic carbonylmetalates of the group 6 and group 8 metals can reduce a number of heteroallenes X=C=Y to coordinated C X ligands, provided X is a first row element (N or O) which can form a strong triple bond with C. Thus Na2M(CO)4 (M = Fe, Ru) and Na2M(CO)5 (M = Cr,W) react readily with COS to give M(CO)5 (M = Fe, Ru) and M(CO)6 (M = Cr,W) in good yield, as established by absorbance mode IR for Fe and W and by isolation of the known derivatives M(CO)4I2 (M = Fe, Ru) and N(n-Bu)4M(CO)5Br (M = Cr, W), while CS2 does not give thiocarbonyl complexes with Na2W(CO)5 or Na2Fe(CO)4. It is suggested on the basis of IR and stoichiometry that the COS reductions are reductive disproportionations leading to thiocarbonate formation. Keywords: Transition metals, Carbonyls, Iron, Rubidinium. (MJM)