Coordination of azol(in)ium dithiocarboxylate ligands to Au(III): unexpected formation of a novel family of cyclometallated Au(III) complexes, DFT calculations and catalytic studies.

A series of cyclometallated gold(III) complexes 21–27 of general formula [Au(dppta)(azdtc)Cl] (dppta = N,N-diisopropyl-P,P-diphenylphosphinothioic amide-κ²C,S; azdtc = azol(in)ium-2-dithiocarboxylate-κ¹S) were prepared and characterized by spectroscopic and diffractometric techniques. Treatment of [Au(dppta)(azdtc)Cl] complexes with methanol led to their quantitative transformation into a novel family of (C^S, S^S)-cyclometallated gold(III) complexes of general formula [Au(dppta)(azmtd)] (azmdt = azol(in)ium-2-(methoxy)methanedithiol-κ²S,S) 28–34. All the [Au(dppta)(azdtc)Cl] complexes 21–27 catalyzed the alkylation of indoles, whereas [Au(dppta)(azmtd)] complexes 28–34 were inactive. Among the synthesized derivatives, complex 22 displayed the highest catalytic activity, leading to a series of functionalized indoles in excellent yields. [ABSTRACT FROM AUTHOR]