Small clusters of low-coordinate late transition metal complexes supported by N-heterocyclic carbene ligands have been synthesized. The metal-metal interactions of these complexes have shown implication for cooperative substrate activation and for multi electron reactions. A series of fluoride-bridged dicopper, disilver, and digold cations supported by the N-heterocyclic carbene ligand SIDipp [1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene] have been synthesized and characterized by X-ray crystallography.  The digold cation displays the lability of the metal fluoride by inserting 3-methyl-1,2-butadiene forming a carbon-fluorine bond.  A hydride-bridged dicopper cation and a hydride-bridged disilver cation supported by an N-heterocyclic carbene  have been synthesized and characterized by X-ray crystallography. Both cations adopt a bent arrangement about the hydride and have a short metal-metal distance. The dicopper hydride cation inserts carbon dioxide to form a (?2-formate)-bridged dicopper cation and inserts phenylacetylene to form a gem-dicopper vinyl cation. The complex also coordinates carbon monoxide reversibly to form a carbonyl adduct. The disilver hydride cation forms a bis (NHC)silver(I) formate when carbon dioxide is added in the form of a Lewis-basic NHC adduct.

Synthesis and reactivity of small clusters of low-coordinate late transition metal complexes supported by N-heterocyclic carbene ligands

248th National Meeting (2014)

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