Dinuclear N-Heterocyclic Dicarbene Gold Complexes in I–III and III–III Oxidation States: Synthesis and Structural Analysis

A series of dinuclear N-heterocyclic bis-dicarbene gold(III) complexes of the general formula [Au 2 Br 4 (RIm-Y-ImR) 2 ](PF 6 ) 2 (Im = imidazol-2-ylidene; 1b, R = Me, Y = CH 2; 2b, R = Me, Y = (CH 2 ) 2; 3b, R = Me, Y = (CH 2 ) 3; 4b, R = Me, Y = (CH 2 ) 4; 5b, R = Cy, Y = CH 2; 6b, R = Me, Y = m -xylylene) were successfully synthesized by oxidative addition of bromine to the corresponding dicarbene gold(I) complexes 1a – 6a . The stability of the digold(III) complexes depends on the length of the bridge Y between the carbene units. The complex with Y = CH 2 undergoes a partial reductive elimination, giving the first example of the mixed-valence gold(I)/gold(III) dinuclear bis-dicarbene complex 1c, together with a minor quantity of the neutral digold(III) mono-dicarbene complex [Au 2 Br 6 (MeIm-CH 2 -ImMe)] ( 1d ). The X-ray crystal structures of complexes 1c, d, 3b, and 6b were determined. Besides complex 3b, the addition of bromine to complex 3a gives complex 3b ′, a coordination metallopolymer, formed by an infinite chain of AuBr 2 units bridged by the dicarbene ligand.