Synthesis and structure of methoxo-terminated molybdenum and tungsten M3S4 clusters containing aminophosphine ligands

Abstract

Trinuclear [M3S4(OCH3)3](edpp)3] + complexes, 1 + (M=Mo) and 2 + (M=W) bearing (2aminoethyl)diphenylphosphine (edpp), have been isolated and fully characterized. Molybdenum and tungsten halide precursors react with methanol in the presence of Et3N, to yield the respective methoxoterminated clusters. The crystal structures of complexes 1 + and 2 + confirm that methoxo ligands are coordinated to the metal centres. Gas-phase dissociation of the novel methoxo cluster cations using ESI tandem mass spectrometry reveals the sequential elimination of three neutral methanol molecules under Collision Induced Dissociation (CID) conditions to form metal/imino M=NH cluster species.

Selective Dehydrogenation of Formic Acid Catalyzed by Air‐Stable Cuboidal PN Molybdenum Sulfide Clusters

“…Each metal atom in 4 + shows a pseudo‐octahedral environment and its coordination sphere includes a phosphorous and a nitrogen atom from the ed i p r p ligand, a chlorine atom, one capping and two bridging sulfur atoms. A relevant feature for this compound is the specific coordination of the aminophosphino ligand in which the three phosphorous atoms are located trans to the capping sulfur atom as observed for other aminophosphino M 3 S 4 (M= Mo, W) clusters [29,33] …”

“…A relevant feature for this compound is the specific coordination of the aminophosphino ligand in which the three phosphorous atoms are located trans to the capping sulfur atom as observed for other aminophosphino M 3 S 4 (M = Mo, W) clusters. [29,33] The solid-state structure of complex 4 + is preserved in solution as evidenced by the 31 P{ 1 H} NMR spectrum registered in CD 2 Cl 2 , which showed a single signal at 53.55 ppm attributed to the three equivalent phosphorous atoms from the aminophosphine ligands which are located above the metal plane (Figure SI1). The cluster C 3 symmetry is evidenced by 1 H NMR spectroscopy where the aminophosphine signals demonstrate that all bidentate ligands are equivalent.…”