Coinage Metal Hydrides: Synthesis, Characterization, and Reactivity

Abstract

Hydride complexes of copper, silver, and gold encompass a broad array of structures, and their distinctive reactivity has enabled dramatic recent advances in synthesis and catalysis. This Review summarizes the synthesis, characterization, and key stoichiometric reactions of isolable or observable coinage metal hydrides. It discusses catalytic processes in which coinage metal hydrides are known or probable intermediates, and presents mechanistic studies of selected catalytic reactions. The purpose of this Review is to convey how developments in coinage metal hydride chemistry have led to new organic transformations, and how developments in catalysis have in turn inspired the synthesis of reactive new complexes.

Ligand-Exchange-Induced Growth of an Atomically Precise Cu29 Nanocluster from a Smaller Cluster

“…Templated growth of nanoclusters has only been observed in a few instances, usually requiring significant thermal activation, and often occurs with major structural rearrangement. 8 28 The effect of C is evident in t spectra (XANE mum absorban peak superimp spectrum of 2 and 2 show we foil, consistent the edge posit sides between (8979.0 eV) an (8980.0 eV) an sistent with an and +1 (Table 1848.9 eV, is in (1851. The rate is mu accelerates as curve fits of th kinetic profiles expected since pseudo-first-or ( Figure 3 inset mechanism in change in a pr ciation with m Cu 26 ) in a kinet mixed-ligand h as [(Ph 2 phen during format ole, [(Ph 2 phen dently by the was isolated on).…”

Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag6H4(dppm)4(OAc)2] and [Cu3H(dppm)3(OAc)2]

“…6,7,16,65,6 bility of compl 2-cyclohexen-5 equiv) to 3 ts), in C 6 D 6 r onding silyl en in small a oduct, 4c. 67 68 or the 1,4-conversion However, selectivity gly, in the m the stoivation has 69 and can of the copequilibrie presence drive the n, we also talyze 1,4-ns. Of the the most We also screened the ability of 1, 2, and [CuH(PPh 3 )] 6 to catalyze the 1,2-hydrosilylation of cyclohexanone (5).…”

Copper(i)-catalysed transfer hydrogenations with ammonia borane

“…[1][2][3][4][5][6]8 Notably, to a much lesser extent has H 3 NBH 3 been employed as a reagent for synthesis, for example in the reduction of functional groups or transfer hydrogenations. [9][10][11] Copper(I) hydride complexes have emerged as powerful catalysts for a wide variety of reductive transformations, generally relying on silanes [12][13][14][15] or, to a much lesser extent, on tin hydrides 16 or dihydrogen 17,18 (Scheme 1). These terminal reducing agents differ conceptually: Si-and Sn-based compounds will deliver a hydride equivalent and the reaction products remain silylated or stannylated until hydrolysis or protonation.…”