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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.

Paula Pérez-RamosMaría A MateoDavid ElorriagaDaniel García-VivóRaquel G SoengasHumberto Rodríguez-Solla
Published in: Dalton transactions (Cambridge, England : 2003) (2024)
A series of cyclometallated gold(III) complexes 21-27 of general formula [Au(dppta)(azdtc)Cl] (dppta = N , N -diisopropyl- P , P -diphenylphosphinothioic amide-κ 2 C,S; azdtc = azol(in)ium-2-dithiocarboxylate-κ 1 S) 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-κ 2 S,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.
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