Dimanganese Bridging Borylene Complexes and their Reactions with Unsaturated Palladium(0) Complexes – Syntheses, Structures and Calculated Properties

The dimanganese bridging borylene complex [μ‐BMes {(η 5 ‐C 5 H 4 Me)Mn(CO) 2 } 2 ] was synthesized from Mes(Cl)BB(Cl)Mes and K[( η 5 ‐C 5 H 4 Me)Mn(CO) 2 H] at low temperature, providing a small sample after manual separation of crystals, allowing a perfunctory spectroscopic analysis, but affording conclusive X‐ray crystallographic structural data. The trimetallic bridging borylene complex [(μ 3 ‐BCl){{(η 5 ‐C 5 H 4 Me)Mn(CO) 2 } {Pd(PCy 3 )} 2 }] was prepared by the addition of [Pd(PCy 3 ) 2 ] to a solution of [μ‐BCl{(η 5 ‐C 5 H 4 Me)Mn(CO) 2 } 2 ], affording pure crystals that were fully characterised including X‐ray crystallographic analysis. The structure is reconciled with detailed theoretical analysis for related model complexes, [(μ 3 ‐BX){{(η 5 ‐C 5 H 5 )Mn(CO) 2 }{Pd(PMe 3 )} 2 }] (X = Me, Cl).