Application of ferrocene-bridged N-heterocyclic carbene stabilised bis-phosphinidenes in Sn(ii) complexation

Abstract

Two new bidentate ferrocene-bridged bis(N-heterocyclic carbene-phospinidenes) (bisNHCPs) were successfully isolated by treating 1,1’-bis-(dichlorophosphine)ferrocene with N-heterocyclic carbenes, followed by dechlorination using sodium naphthalenide. The bisNHCPs were used in complexation of various...

Synthesis and Reactivity of Bidentate N‐Heterocyclic Carbene‐Phosphinidene Supported Si(IV) Dicationic Complexes

“…The positive charge is delocalized, hence stabilized in the NHC ring system. Analogue bond elongation/shortening has been reported in the bis(NHCP)‐stabilized Sn(II) complex [26] . The sum of bond angles around P1 and P2 are 319.76° and 320.96° respectively, accounting for a trigonal pyramidal coordination of the phosphorus atoms.…”

“…The sum of bond angles around P1 and P2 are 319.76° and 320.96° respectively, accounting for a trigonal pyramidal coordination of the phosphorus atoms. Similarly to the free bis(NHCP) as well as the reported bis(NHCP)‐supported stannyliumylidene complex, the mesityl substituents show a sandwich π–π stacking interaction with the Cp ring of the ferrocene visible in the SC‐XRD structure [26] . Furthermore, the molecular structure of dication [ 2 b ] displays a sandwich π–π stacking interaction between the second mesityl substituent and the Si‐bonded phenyl rings.…”

“…Analogue bond elongation/shortening has been reported in the bis(NHCP)-stabilized Sn(II) complex. [26] The sum of bond angles around P1 and P2 are 319.76°and 320.96°respectively, accounting for a trigonal pyramidal coordination of the phosphorus atoms. Similarly to the free bis(NHCP) as well as the reported bis(NHCP)-supported stannyliumylidene complex, the mesityl substituents show a sandwich π-π stacking interaction with the Cp ring of the ferrocene visible in the SC-XRD structure.…”

“…Recently, the first two examples of bis( N ‐heterocyclic carbene‐phosphinidene) (bis(NHCP)) ligands have been reported [25–26] . Their coordination capabilities have been demonstrated by formation of stable Ge(II), Sn(II), and transition metal halide (CuCl, ZnI 2 , FeCl 2 ) complexes.…”

A Nucleophilic Tin(II) Cation Salt

“…[55][56][57][58] Previous attempts by Inoue for coordination of a bisNHCP Sn(II) cation (bisNHCP = ferrocenebridged N-heterocyclic carbene stabilized bis-phosphinidenes) with CuCl only gave a transmetalation product. 98 The group of Majumdar attempted to establish nucleophilic behavior of a bis(a-iminopyridine)-stabilized Sn 2+ toward TMs but they were unsuccessful as well. 53 The success in isolating 5[OTf] demonstrates a straightforward synthetic method for coinage metal Sn(II) cation complexes.…”