Abstract
Reactions of a new imido phosphido complex, Cp2Nb(═NBut)(PPh2) (1), with olefin complexes of rhodium afford two types of compounds. With [(μ-Cl)Rh(C2H4)2]2, an imido/phosphido-bridged complex, Cp(Cl)Nb(μ-NBut)(μ-PPh2)RhCp (2), characterized by NMR and X-ray diffraction, was prepared. Formation of 2 represents a rare example of a Cp/Cl exchange reaction in organometallic chemistry. When 1 reacts with [(μ-Cl)Rh(COD)]2, the target phosphido-bridged bimetallic complex Cp2Nb(═NBut)(μ-PPh2)Rh(Cl)(COD) (4) is formed. The structure of this product was established by NMR and an X-ray diffraction study. Both 2 and 4 are catalyst precursors for hydrosilylation of benzaldehyde and acetophenone. The activity of the neutral complex 4 exceeds that of the cation [Cp2Nb(NBut)(PPh2)Rh(COD)]+ derived from 4 by chloride anion abstraction.
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