Tetraethyl diphosphite-bridged binuclear carbonyl derivatives of decacarbonyldimanganese and pentacarbonylmanganese halides

Abstract

Reactions of (EtO)₂POP(OEt)₂(tedip) with [Mn₂(CO)₁₀] led to complex mixtures from which [Mn₂(CO)₈(µ-tedip)](1) and [Mn₂(CO)₆(µ-tedip)₂](2) were identified as major products. However, the reactions of tedip with [MnX(CO)₅](X = Br or I) were more dependent on experimental conditions and could lead to either [Mn₂X₂(CO)₈(µ-tedip)](3), [Mn₂(µ-X)₂(CO)₆(µ-tedip)](4), [Mn₂X₂(CO)₆(µ-tedip)₂](5), or [Mn₂(µ-X)₂(CO)₄(µ-tedip)₂](6), in all of which the tedip ligand is bridging. Other minor products not completely characterized were also observed. Rhenium analogues of compounds (4) and (6) were also obtained from [ReBr(CO)₅] and tedip. An extension of this study to the reactions of Ph₂PCH₂PPh₂(dppm) with [MnX(CO)₅](X = Cl, Br, or I) revealed that binuclear dppm-bridged complexes analogous to compounds (4) can be obtained under appropriate conditions.