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

Abstract

ABSTRACT:The group 11 hydride clusters [Ag 6 H 4 (dppm) 4 (OAc) 2 ](1) and(2) (dppm = 1,1-bis(diphenylphosphino)methane) were synthesized in moderate yields from the reaction of M(OAc) (M = Ag, Cu) with Ph 2 SiH 2 , in the presence of dppm. Complex 1 is the first structurally characterized homometallic polyhydrido silver cluster to be isolated. Both 1 and 2 catalyze the hydrosilylation of (,-unsaturated) ketones. Notably, this represents the first example of hydrosilylation with an authentic silver hydride complex.

Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity

“…Electrospraying a solution of [Ag 3 (H/D)(L Cy ) 3 ](PF 6 ) 2 in acetonitrile gave rise to major mass signals at m / z 775.31 and 775.81 (most abundant masses), assigned to the molecular dication [ P ] 2+ , which is confirmed by the excellent agreement between the experimental and simulated isotope patterns (calcd: m / z 775.32 and 775.83, respectively, see insets to Figures b and Figure S11). The lack of further dissociation products demonstrates the stability of this hydrido/deuterido silver(I) complex under electrospray ionization (ESI) conditions, in accordance with other observations on the [M 3 (μ 3 ‐H)] (M=Cu, Ag) structural motif –…”

“…Recently, the first monoligated dimeric copper hydrides were isolated by using N‐heterocyclic carbene (NHC) ligands . The key chemical transformations that are mediated by CMHs encompass reduction reactions, for example, the hydrogenation of carbonyl compounds or CO 2 , as well as hydrosilylations (ketones) and other hydrogenations (alkenes and alkynes) . In catalytic studies the application of copper hydrides dominates today, but interesting perspectives on silver and gold or heterometallic species have been reported and have gained in importance on account of their distinctive (photo)reactivity .…”

“…Thus, the expected stability of [ P ] 2+ facilitates parallel studies in the gas phase and in solution. Finally, we note in passing that recently there has been growing interest in the preparation of (atomically precise) ligand‐protected silver subnano‐ and nanoclusters by the reduction of silver(I) salts with NaBH 4 , with the emphasis on [ P ] 2+ being a potential intermediate in cluster growth or a building block of larger entities …”

A Fluxional Cu8H6 Cluster Supported by Bis(diphenylphosphino)methane and its Facile Reaction with CO2

“…[14] Haytone tal. [15] However,the average Cu···Cu distance of 2.91 is appreciably longer than that of 2, presumably due to different number and coordination mode of the carboxylate ligands. [15] However,the average Cu···Cu distance of 2.91 is appreciably longer than that of 2, presumably due to different number and coordination mode of the carboxylate ligands.…”

Synthesis and X‐Ray Crystallographic Characterisation of Frustum‐Shaped Ligated [Cu18H16(DPPE)6]2+ and [Cu16H14(DPPA)6]2+ Nanoclusters and Studies on Their H2 Evolution Reactions

“…There are a number of structurally characterised polyhydrido copper and silver NCs, where the rare kernel examples are Cu 0 NCs or chiral Cu NCs . The synthesis of unknown metal kernels can provide insight into the growth mechanism of large nanoparticles .…”