NDLI: Coinage metal complexes with bridging hybrid phosphine–NHC ligands: synthesis of di- and tetra-nuclear complexes

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Braunstein, Pierre Simler, Thomas Danopoulos, Andreas A.
Description	Author Affiliation: Simler T ( Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, 67081 Strasbourg Cedex, France.); Braunstein P ( Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, 67081 Strasbourg Cedex, France.); Danopoulos AA ( Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, 67081 Strasbourg Cedex, France and Institute for Advanced Study (USIAS), Université de Strasbourg, 4 rue Blaise Pascal, 67081 Strasbourg Cedex, France. braunstein@unistra.fr danopoulos@unistra.fr.)
Abstract	A series of P–NHC-type hybrid ligands containing both $PR_{2}$ and N-heterocyclic carbene (NHC) donors on meta-bis-substituted phenylene backbones, $L^{Cy},$ $L^{tBu}$ and $L^{Ph}$ (R = Cy, tBu, Ph, respectively), was accessed through a modular synthesis from a common precursor, and their coordination chemistry with coinage metals was explored and compared. Metallation of $L^{Ph}·n(HBr)$ (n = 1, 2) with $Ag_{2}O$ gave the pseudo-cubane $[Ag_{4}Br_{4}(L^{Ph})_{2}],$ isostructural to $[Ag_{4}Br_{4}(L^{R})_{2}]$ (R = Cy, tBu) (T. Simler, P. Braunstein and A. A. Danopoulos, Angew. Chem., Int. Ed., 2015, 54, 13691), whereas metallation of $L^{R}·HBF_{4}$ (R = Ph, tBu) led to the dinuclear complexes $[Ag_{2}(L^{R})_{2}](BF_{4})_{2}$ which, in the solid state, feature heteroleptic Ag centres and a ‘head-to-tail’ (HT) arrangement of the bridging ligands. In solution, interconversion with the homoleptic ‘head-to-head’ (HH) isomers is facilitated by ligand fluxionality. ‘Head-to-tail’ $[Cu_{2}Br_{2}(L^{R})_{2}]$ (R = Cy, tBu) dinuclear complexes were obtained from $L^{R}·HBr$ and $[Cu_{5}(Mes)_{5}],$ Mes = 2,4,6-trimethylphenyl, which also feature bridging ligands and heteroleptic Cu centres. Although the various ligands $L^{R}$ led to structurally analogous complexes for R = Cy, tBu and Ph, the rates of dynamic processes occurring in solution are dependent on R, with faster rates for R = Ph. Transmetallation of both NHC and P donor groups from $[Ag_{4}Br_{4}(L^{tBu})_{2}]$ to $Au^{I}$ by reaction with [AuCl(THT)] (THT = tetrahydrothiophene) led to $L^{tBu}$ transfer and to the dinuclear complex $[Au_{2}Cl_{2}L^{tBu}]$ with one $L^{tBu}$ ligand bridging the two Au centres. Except for the silver pseudo-cubanes, all other complexes do not exhibit metallophilic interactions.
ISSN	14779226
Issue Number	12
Journal	Dalton Trans.
Volume Number	45
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2016-03-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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