Formation of Dinuclear AuII and AuI/AuIII Mixed-Valence Complexes is Directed by Structural Constraints Imposed by Cyclophane-NHC Ligands

被引：17

作者：

Mageed, Ahmed H. ^{[1
,2
]}

Skelton, Brian W. ^{[1
,3
]}

Sobolev, Alexandre N. ^{[3
]}

Baker, Murray V. ^{[1
]}

机构：

[1] Univ Western Australia, Sch Mol Sci, Chem M310,35 Stirling Highway, Perth, WA 6009, Australia

[2] Univ Kufa, Fac Sci, Dept Chem, POB 21, An Najaf 54001, Iraq

[3] Univ Western Australia, Ctr Microscopy Characterisat & Anal M310, Perth, WA 6009, Australia

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2018年 / 01期

关键词：

Gold; Carbenes; Multinuclear complexes; Oxidation; Mixed-valent complexes; Cyclophanes; DI(N-HETEROCYCLIC CARBENE) LIGANDS; HETEROCYCLIC DICARBENE LIGANDS; GOLD(I) COMPLEXES; OXIDATIVE ADDITION; QUANTUM YIELD; AU(I); AUROPHILICITY; LUMINESCENCE; REACTIVITY; BIDENTATE;

D O I：

10.1002/ejic.201701272

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The oxidation of dinuclear Au-I complexes containing cyclophane-bis(NHC) ligands by SOCl2, Br-2 and I-2 has been investigated. The outcome of the oxidation was dependent on the nature of the cyclophane-NHC framework. The new complexes were fully characterised by X-ray diffraction and H-1 and C-13 NMR spectroscopy. When the Au-I complex contained an ortho-cyclophane framework (dictating short intra-cation Au center dot center dot center dot Au distances), oxidation resulted in dinuclear Au-II complexes of the form X-Au-II(NHC)(2)-Au-II(NHC)(2)-X (X = Cl, Br, I), the Au center dot center dot center dot Au distance being in the range 2.6055(3)-2.6501(1) angstrom. These Au-II complexes are strongly luminescent. When the Au-I complex contained an meta-cyclophane framework (dictating longer intra-cation Au center dot center dot center dot Au distances), oxidation with SOCl2 or Br-2 resulted in dinuclear complexes containing Au-I and Au-III centres of the form X-Au-III(NHC)(2)-X-Au-I(NHC)(2). NMR studies showed that interconversion of the Au-I and Au-III sites within the complexes occurred at rates comparable to the NMR timescale.

引用

页码：109 / 120

页数：12