Issue 16, 2025

Changing the properties of monodentate and P,C-chelating ferrocenyl-substituted 1,2,3-triazol-5-ylidene ligands through an inserted carbonyl moiety

Abstract

Triazolylidenes derived from readily accessible triazoles are useful ligands for coordination chemistry and catalysis. This work describes the synthesis of Group 11 metal complexes of new ferrocenyl-substituted triazolylidene ligands in which the ferrocene and triazolylidene moieties are separated by a carbonyl linker. In particular, complexes of types [MCl(FcC(O){CCN(Mes)NN(Me)}-κC5)] (M = Cu or Au; Fc = ferrocenyl) and [M(FcC(O){CCN(Mes)NN(Me)}-κC5)2][BF4] (M = Cu, Ag, or Au) were prepared from FcC(O)C[triple bond, length as m-dash]CH and characterised by spectroscopic methods, X-ray diffraction analysis and cyclic voltammetry. Using a similar strategy, the Pd(II) complex trans-[PdCl2(Ph2PfcC(O){CCN(Mes)NN(Me)}-κ2P,C5)] (fc = ferrocene-1,1′-diyl) was synthesised and analogously characterised. The phosphinocarbene ligand in this compound coordinates as a trans P,C-chelating ligand, unlike its analogues that lack the C[double bond, length as m-dash]O spacer and similar compounds that combine the phosphine and carbene donor groups on the ferrocene scaffold. The influence of the carbonyl spacer was evaluated in a pair of Pd(II) bis-carbene complexes, [PdBr2({C(Fc)CN(Mes)NN(Me)}-κC5)(iPr2-bimy)] and [PdBr2(FcC(O){CCN(Mes)NN(Me)}-κC5)(iPr2-bimy)] (iPr2-bimy = 1,3-diisopropyl-1,3-dihydro-2H-benzimidazol-2-ylidene), by Huynh's electronic parameters and the FeII/FeIII redox potential from cyclic voltammetry, which suggested an electron density decrease at the ferrocenyl group and decreased σ donor ability of the triazolylidene moiety upon introduction of the C[double bond, length as m-dash]O linker. The Group 11 metal complexes were tested as catalysts for the metal-catalysed cyclisation of N-propargylbenzamide into 2-phenyl-5-methylene-4,5-dihydrooxazole. Among them, the chlorogold complex activated with a silver salt achieved the best results.

Graphical abstract: Changing the properties of monodentate and P,C-chelating ferrocenyl-substituted 1,2,3-triazol-5-ylidene ligands through an inserted carbonyl moiety

Supplementary files

Article information

Article type
Paper
Submitted
06 Mar 2025
Accepted
21 Mar 2025
First published
24 Mar 2025
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2025,54, 6563-6575

Changing the properties of monodentate and P,C-chelating ferrocenyl-substituted 1,2,3-triazol-5-ylidene ligands through an inserted carbonyl moiety

V. Varmužová, I. Císařová and P. Štěpnička, Dalton Trans., 2025, 54, 6563 DOI: 10.1039/D5DT00545K

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