title: 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.
authors.affiliation: Instituto Universitario de Tecnología Química CSIC-UPV, Universidad Politécnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia, Spain. hgarcia@qim.upv.es grirrane@itq.upv.es acorma@itq.upv.es.
authors.forename: A
authors.initials: A
authors.lastname: Grirrane
authors.forename: E
authors.initials: E
authors.lastname: Álvarez
authors.forename: J
authors.initials: J
authors.lastname: Albero
authors.forename: H
authors.initials: H
authors.lastname: García
authors.forename: A
authors.initials: A
authors.lastname: Corma