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.

The first synthesis of an isocyanide-functionalized imidazolium salt and transition metal complexes thereof.

An isocyanide-functionalized imidazole was obtained from 4-(1H-imidazol-1-yl)aniline by the Ugi method and subsequently transformed into the corresponding imidazolium salt by treatment with MeI. Coordination of the isocyanide residue allowed the synthesis of several transition metal complexes containing a peripheral imidazolium cation, which are suitable starting materials for the formation of mixed ligand isocyanide-NHC heterometallic complexes.

A new approach to the synthesis of trinuclear gold(i) imidazolate complexes and their silver(i)-induced photoluminescence behavior.

New trinuclear gold(i) N-arylimidazolate cluster complexes have been synthesized from cationic [Au(CNR)2]+ isocyanide complexes and their structure and photoluminescence behavior have been compared with those of their 1-methylimidazolate counterpart. A drastic change in their photophysical properties was observed upon coordination of the Ag+ cation.

Selective formation of formamidines, carbodiimides and formimidates from isocyanide complexes of Mn(i) mediated by Ag2O.

The isocyanide ligands in complexes fac-[Mn(CNR)(bipy)(CO)3]+ are selectively transformed into formamidines, carbodiimides and formimidates upon nucleophilic addition of NH2Me or alkoxides and subsequent treatment with Ag2O, which promotes tautomerization or oxidation processes of the former carbene ligands.