Electron rich acetylide clusters; molecular and electronic structure and reactions of Os₃(CO)₇(µ₂-η²-CCR)₂(µ-PPh₂)₂(R = Ph, Prⁱ); 50-electron species with expanded metal frameworks

Abstract

The reactivity of the 50-electron acetylide clusters Os3(CO)7(µ2-η2-CCR)2(µ-PPh2)2[(1a) R = Ph; (1b) R = Pri] which have unusual expanded Os3 frameworks, is dominated by nucleophilic addition at the metals: the molecular structures of Os3(CO)7(µ2-η2-CCPri)2(µ-PPh2)2 and the ethylamine adduct of (1a), Os3(CO)6(µ2-η2-CCPh)(η1-CCPh)(µ-PPh2)2(EtNH2)2(2a) have been determined by X-ray diffraction and their electronic structures probed by EHMO calculations.