Di- and Trinuclear Complexes of Pd(0) and Pt(0) with Bridging Silylene Ligands: Structures with a Coordinatively Unsaturated Metal Center and Their Reactions with Alkynes

Abstract

Reactions of Et 2 NSiPh 2 B(pin) with [Pd(PCy 3 ) 2 ] and [Pt(PCy 3 ) 2 ] produce dinuclear Pd(0) and Pt(0) complexes bearing a bridging diphenylsilylene ligand, [{M 1 (PCy 3 )}-{M 2 (PCy 3 ) 2 }(μ-SiPh 2 )] (1

Silyliumylidene Ion Stabilized by Two σ‐Donating Ni(0)‐ and Pd(0)‐Fragments

“…The structure also shows short Si‐Ni [2.132(1) Å] and Si‐Pd [Si1‐Pd1 2.268(1) Å] bond lengths, and a Pd‐Ni bond [2.599(1) Å] only slightly longer than that observed for 2 [2.559(1) Å]. The related mono‐silylene‐bridged binuclear Pd(0) 2 ‐complexes, synthesized by Osakada [Ph 2 SiPd 2 (PCy 3 ) 3 ] [28] and by Kira [R 2 SiPd 2 (PMe 3 ) 2 ], [29] presents similar geometries with Si‐Pd bond lengths [2.289–2.307 Å], significantly shorter than those observed for bis‐silylene‐bridged Pd(0) 2 ‐complexes (2.382–2.400 Å) [30] . As Ni(0)‐based binuclear‐complexes, only one example of bis‐silylene‐bridged Ni(0) 2 ‐complex [Si‐Ni: 2.280–2.309 Å] is known [31] and, to the best of our knowledge, neither mono‐silylene‐bridged Ni(0) 2 ‐ nor heterobinuclear Pd(0)‐Ni(0)‐complexes have not been described so far.…”

“…[2.132(1) Å] and Si-Pd [Si1-Pd1 2.268(1) Å] bond lengths, and a Pd-Ni bond [2.599(1) Å] only slightly longer than that observed for 2 [2.559(1) Å]. The related mono-silylene-bridged binuclear Pd(0) 2 -complexes, synthesized by Osakada [Ph 2 SiPd 2 (PCy 3 ) 3 ][28] …”