Synthesis and Structure of the Decanuclear Gold(I) Cluster Cation [Au8(AuCl)2{μ3-P(tBu)}2{μ-P(tBu)=C(NMe2)2}6]4+ with Bridging Phosphaalkene and Phosphanediide Ligands

Abstract

Reaction of the inversely polarized phosphaalkene HP=C(NMe2)2 (1) with [AuCl(PPh3)] (2a) in a molar ratio of 2:1 in THF led to the formation of complex [Au{HP=C(NMe2)2}2]Cl (3) as a pale yellow solid. In contrast to this, treatment of 2a with two molar equivalents of tBuP=C(NMe2)2 (4) afforded a mixture of [Au{P(tBu)=C(NMe2)2}2]+Cl− (5) and [{(Me2N)2C=(tBu)PAu}2(μ‐Cl)]+Cl− (6). In CH2Cl2 solution this mixture was slowly converted into the novel decanuclear complex [Au8(AuCl)2{μ3‐P(tBu)}2{μ‐P(tBu)=C(NMe2)2}6]4+(Cl−)4 (7) featuring six edge‐bridging phosphaalkene ligands and two μ3‐tert‐butylphosphanediide ligands. In solution the cluster 7 shows a high order 31P{1H} NMR spectrum of the [AB2C]2 type. According to the X‐ray structural analysis the Au10 framework may be described as a slightly puckered ladder constructed of three quadrangles. The central Au4 parallelogram is capped on both faces by a pair of [tBuPAuCl] units. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

N‐Heterocyclic Carbene–Phosphinidene Complexes of the Coinage Metals

“…These species might dimerize and self‐assemble to give tetrameric structures, such as {[(Ph 3 P)Au] 2 (μ‐Cl)} 2 [SbF 6 ] 2 , which displays comparatively long Au⋅⋅⋅Au distances of ≈3.66 Å within the monomeric cation {[(Ph 3 P)Au] 2 (μ‐Cl)} + , but short unsupported Au⋅⋅⋅Au distances of ≈3.07 Å between the monomeric units 51. Likewise, several short Au⋅⋅⋅Au distances were also found in a decanuclear gold(I) cluster, which contained the acyclic carbene–phosphinidene (Me 2 N) 2 C⋅P t Bu 52…”

Unusual Phosphorus−Phosphorus Double Bond Contraction upon Mono- and Di-auration of a Diphosphene

“…Possible explanations for the structural impacts of these Lewis acids on a diphosphene are explicated. Such effects do not appear to have been reported for aurated phosphaalkenes that are receiving increased attention. − …”

“…Such effects do not appear to have been reported for aurated phosphaalkenes that are receiving increased attention. [21][22][23][24][25][26][27]…”

Gold Phosphide Complexes

“…36-38 which display a tetrahedral environment at the phosphorus atom and intramolecular Au-Au distances in general longer than twice the van der Waals radium of gold (1.66 Å). 39 Only in the case of the bulkier phosphodiide ligand P(2,4,6-C 6 H 2 t Bu 3 )…”