Synthesis, structure, and reactions of a copper–sulfido cluster comprised of the parent Cu₂S unit: {(NHC)Cu}₂(μ-S)

Abstract

The first CuI2(μ-S) complex, {(IPr*)Cu}2(μ-S) (IPr* = 1,3-bis(2,6-(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene), has been synthesized, and its structure has been characterized crystallographically.

Stable ‐ESiMe3 Complexes of CuI and AgI (E=S, Se) with NHCs: Synthons in Ternary Nanocluster Assembly

“…The molecularstructure of [(IPr)AgÀSSiMe 3 ] 1 (elipsoidsset at 40 % probability;h ydrogen atoms are omitted);Selectedbondlengths[ ] and angles [8]: C1-Ag1 2.089(6), Ag1-S12 .341(2), S1-Si1 2.093(3); C1-Ag1-S1 175.2(2), Ag1-S1-Si1 101.6(1). (5) 16.151 (5) 16.572 (3) 24.602(7)2 1.819(6)21.289(4) a [8]67.516(13)68.375 (15) 88.030 (8) 90 90 90 b [8]79.534 (12)78.886(13) 66.251 (8) 94.930 (13) 101.334 (10) 100.093(10) g [8]71.104 (9) 71.154 (11) 87.115 (9) 90 90 90 V [ 3 ]1800. 8(9) 1839.9(10) 3567.8 (11)…”

“…[8] More recently,Z hai and coworkersr eported the synthesis of the dimetallic Cu I 2 (m-S) complex via ligation of the bulkierc arbene 1,3-bis(2,6-(diphenylmethyl)-4-methlphenyl)imidazol-2-ylidene as the ancillary ligand. [9] In this vein, access to ar ange of [(NHC)MÀESiMe 3 ]( NHC = Nheterocyclic carbene;M= Cu, Ag;E= S, Se) is of fundamental importance for the formation of new ternary metal chalcogenide nanocluster architectures. For ac omparison with the recently reported [(IPr)CuÀESiMe 3 ] [8] and to evaluate the influence of metal or ancillary ligand change on the structural features and thermalstability,herein we report the synthesis, crystal structures, and spectroscopicc haracterization of the new silver(I)a nd copper(I) (trimethylsilyl)chalcogenolates stabilized with IPr and (iPr 2 -bimy), respectively:[ (IPr)AgÀESiMe 3 ]( E= S, 1; E = Se, 2)a nd [(iPr 2 -bimy)CuÀESiMe 3 ] 2 (E = S, 4;E = Se, 5).…”

Probing the electronic and mechanistic roles of the μ4-sulfur atom in a synthetic CuZ model system

“…13,14 Among the synthetic copper compounds and materials known to activate N 2 O, [15][16][17][18] one of our groups has reported the only examples of N 2 O activation by copper sulde clusters. In one case, a dicuprous [Cu 2 S] cluster with an unsupported m 2 -sulde bridge 19 was found to reduce multiple N 2 O equivalents to N 2 , resulting in exhaustive oxidation of the sulfur center to a m 2 -sulfate ligand (Scheme 1a). 20 Here, the copper centers remained redox inactive while the m 2 -sulde ligand was not only the redox-active center but also acted as an oxygen atom acceptor.…”

NHC copper complexes functionalized with sulfoxide and sulfone moieties

“…Examples of mixed copper compounds were presented by Zhai's group and Owen's group. These complexes were formed as copper sulfide clusters bearing {(NHC)Cu}2(μ‐S) unit or they have contained a ditopic bis‐thione ligand. Unfortunately, no catalytic activities of these complexes were detected.…”