Syntheses, structures, and reactions of trimeric and tetrameric alkoxotricarbonylmanganese complexes

Abstract

Bromopentacarbonylmanganese reacts with SnMe₃(OR)(R = Me, Et, Prⁿ, Prⁱ, Buⁿ, C₆H₁₁, CH₂CHCH₂, or CH₂Ph) to form the complexes [{Mn(OR)(CO)₃}₃], and in the case of benzyl the tetramer [{Mn(OCH₂Ph)(CO)₃}₄] is also formed. The structure of the trimers is based on a scalene triangle of manganese atoms, with face- and edge-bridging alkoxide groups. The tetramer is a cube of manganese and oxygen atoms with only face-bridging alkoxide groups. The complex [{Mn(OEt)(CO)₃}₃] reacts with PMe₂Ph, PhOH, and PhSH to give respectively [Mn₃(OEt)₃(CO)₈(PMe₂Ph)], [Mn₃(OEt)₂(OPh)(CO)₉], and [{Mn(SPh)(CO)₃}₄].