Construction of two novel tungsten(VI)–silver(I) mixed metal clusters controlled by bis(diphenylphosphino) methane and coordinated inorganic anions

By the reaction of [Ag3(dppm)3I2]I with (NH4)2WS4 in MeCN/DMF (1:1), a trigonal bipyramid-shaped cluster [Ag3 I (dppm)2 WS4] (1) was isolated [dppm = bis (diphenylphosphino) methane]. By the reaction of (NH4)2WS4 with AgSCN and dppm in MeCN/DMF (1:1) in the presence of 1,10-phenathroline, an insect-shaped cluster [Ag4 (SCN)2 (dppm)4WS4]·H2O (2) was synthesized. Compounds 1 and 2 were characterized by single-crystal X-ray diffraction, luminescence, IR, UV–Vis, 1H and 31P NMR spectroscopy. In 1, WS 4 2 - and μ3-I are coordinated to three Ag atoms, which are further bridged by two dppm ligands. In 2, Ag1 and Ag4 are coordinated by two P atoms from two dppm ligands, one μ3-S from WS 4 2 - and one S atom from SCN− while Ag2 and Ag3 are coordinated by one μ2-S atom and one μ3-S atom from WS 4 2 - , two P atoms from two dppm ligands.