Structural Divergence in the Products of the Reaction of [MoCl(η³-C₃H₅)(CO)₂(dmpm)] with Nucleophiles

Abstract

The complex [MoCl(η3-allyl)(CO)2(dmpm)] (dmpm = bis(dimethylphosphino)methane) (1) reacts with sodium azide and with sodium cyanide to afford the new complexes [Mo(N3)(η3-allyl)(CO)2(dmpm)] (2) and [Mo(CN)(η3-allyl)(CO)2(dmpm)] (3), respectively, which were characterized spectroscopically and by X-ray diffraction. Complex 2 is a cis-dicarbonyl in which one of the P atoms of dmpm is approximately trans to a carbonyl, and the other is trans to the allyl. In contrast, 3 is a rare trans-dicarbonyl. A theoretical analysis was applied to rationalize this difference.