Multinuclear silver(i) XPhos complexes with cyclooctatetraene: photochemical C–C bond cleavage of acetonitrile and cyanide bridged Ag cluster formation

Abstract

Cationic mono-, di-, tri- and tetra-nuclear silver complexes with Buchwald-type phosphane (XPhos) and cyclooctatetraene (COT) have been synthesized and characterized. Formation of [(XPhos-Ag)n(COT)][SbF6]n (n = 1 and 2) complexes was confirmed by single-crystal X-ray crystallography and multinuclear NMR spectroscopy. Variable-temperature NMR spectroscopy in CD2Cl2 solution shows the fluxionality of the COT ring in the mono-Ag(i) XPhos complex. Fluxionality of COT was also confirmed in the case of the di-Ag(i) XPhos complex by solid-state and solution (31)P NMR spectroscopy. The C-C bond cleavage of coordinated acetonitrile [XPhos-Ag(i)-NCCH3] resulting in cyanide bridged Ag cluster formation [(XPhos-Ag)2(μ-CN)n(μ-Ag)n-1] (n = 1, 2, 3 and 4) upon light excitation of [(XPhos-Ag)n(COT)] was confirmed by HRESI-MS, UV-Absorption and HR-TEM.

Gold(I) and Silver(I) π-Complexes with Unsaturated Hydrocarbons

“…For a long time, the triphenylphosphine–gold π-complexes were considered unstable in solution. , However, we have recently shown that these complexes are much more stable than what was previously published and we were also able to characterize them by X-ray for the first time . Other silver­(I) and gold­(I) π-complexes utilizing phosphines and other ligands were characterized previously as well. − …”

Structure–function correlation of mononuclear nonheme copper(ii) compounds based on a ligand backbone effect and phenoxazinone synthase activity

“…5) showed a prominent peak at 445.08, which corresponded to [Cu(BQPN)(CN)] 1+ (calcd m / z 445.13). 42…”

Direct transformation of nitriles to cyanide using chloride anion as catalyst

“…1e and f), 11 ligand design molecular recognition (Fig. 1g and h), 12,13 photo-assisted oligomer cyanation, 14 and hydrothermal metal-mediated compoundation 15 were also attempted for the activation of nitriles. However, all the above reactions were restricted to the stoichiometric splitting of nitriles, with the generated cyanide anion binding to the catalysts.…”