ChemInform Abstract: Copper(I) Complexes Bearing Carbenes Beyond Classical N‐Heterocyclic Carbenes: Synthesis and Catalytic Activity in “Click Chemistry”.

Abstract

Chemistry". -(BIDAL, Y. D.; LESIEUR, M.; MELAIMI, M.; NAHRA, F.; CORDES, D. B.; ATHUKORALA ARACHCHIGE, K. S.; SLAWIN, A. M. Z.; BERTRAND, G.; CAZIN*, C. S. J.; Adv. Synth. Catal. 357 (2015) 14-15, 3155-3161, http://dx.

Tuning the Metal/Chalcogen Composition in Copper(I)–Chalcogenide Clusters with Cyclic (Alkyl)(amino)carbene Ligands

“…22a Reactions of equimolar amounts of 1 and E(SiMe 3 ) 2 in THF at −30 °C followed by extraction of the product into hydrocarbons, filtration, and removal of the solvent yield analytically pure [(CAAC Cy )CuESiMe 3 ] (E = S, 2a; E = Se, 2b) as thermally stable off-white solids in 41 and 62% yield, respectively (Scheme 1). Based on the similarity in steric bulk between IPr (%V bur = 47.6) 25 and CAAC Cy (44.8%), 26 we propose mononuclear linear complexes, similar to [(IPr)CuESiMe 3 ]. 19a The 1 H NMR spectra of 1 and 2 are consistent with the proposed linear structures (ESI).…”

N-Heterocyclic Carbene Complexes of Copper, Nickel, and Cobalt

“…33 Recently, the scope of the Cu 2 O method was further broadened to encompass azolium salts precursors of mesoionic, cAAC, and BAC NHCs (see below). 34,35 Other bulky imidazol-2-ylidenes have been designed to take advantage of the unique steric opportunities provided by the ligand framework. The "flexible" sterics of IPr*, IPr* , and ITr have raised interest for their use as spectator ligands in Cu bioinspired coordination chemistry (see, for example, Cu-(NHC), thioalkoxides, and thiophenoxides in section 2.2.1.1.3).…”

“…The triazolylidene complex 4 Cu became accessible by deprotonation of the triazolium precursor in the presence of CuI, 40 while the related family of chlorides 5 Cu was obtained by transmetalation from analogous silver complexes with CuCl; 41 complex 6 Cu was accessed from the triazolium °C and microwave heating. 35 The same methodology under optimized conditions was also used for the synthesis of the mesoionic imidazol-4-ylidene complex 7 Cu (toluene 110 °C, 24 h) and the bis(diisopropylamino)cyclopropenylidene (BAC) complex [CuCl(BAC)] ( 8Cu ) (MeCN, 2 h, microwave heating). 34 Mononuclear complexes with the six-and sevenmembered extended ring NHCs 9 Cu and 10 Cu were prepared by transmetalation of the ligand from analogous AgBr complexes (accessible from azolium bromides with Ag 2 O) to CuBr or by reaction of the in situ generated ligand with CuCl (Scheme 5).…”