Triangular thiocomplexes of molybdenum: reactions with halogens, hydrohalogen acids and phosphines

• Published in: Inorganica Chimica Acta Vol. 167; no. 1; pp. 39 - 45
• Main Authors: Fedin, V.P., Sokolov, M.N., Mironov, Yu.V., Kolesov, B.A., Tkachev, S.V., Fedorov, V.Ye
• Format: Journal Article
• Language: English
• Published: Lausanne Elsevier B.V 02.01.1990; Elsevier Science
• Subjects: Chemistry; Coordination compounds; Exact sciences and technology; Inorganic chemistry and origins of life; Preparations and properties; Thio complex; Ammonium Compounds; Tertiary phosphine; Trinuclear complex; Anionic complex; Transition metal Complexes; Mu complex; Addition reaction; Infrared spectrum; Chemical reactivity; NMR spectrum; Raman spectrum; Molybdenum Complexes; Halo complex; Thiomolybdates
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/S0020-1693(00)83936-5

The triangular (NH 4) 2Mo 3S 13·2H 2O complex interacts with Cl 2 and Br 2 in CH 3CN and with concentrated hydrohalogen acids HX (X = Cl, Br and I) retaining its Mo 3(μ 3-S)(μ-S 2) 3 4+ cluster fragment to produce the Mo 3(μ 3-S)(μ 2-S 2) 3X 6 2− complexes in high yields. IR and Raman spectra of the Mo 3S 7X 6 2− complexes have been studied. Salts of Mo 3S 7X 6 2− (X = Cl, Br) containing 92Mo, 100Mo and 34S isotopes and compounds with μ 2-( 32S- 34S) ligands have been also synthesized. For Mo 3S 7Cl 6 2−, an analysis of the normal vibrations has been performed. The Mo 3S 7X 6 2− complexes (X = Cl, Br) interact with phosphines (PPh 3 and dppe). The reactions proceed with elimination of the μ 2-S 2 sulfurs to form sulfides of the phosphines and the phosphine complexes Mo 3S 4X 4·3PPh 3 and Mo 3S 4X 4·3dppe containing a Mo 3S 4 4+ cluster fragment. It has been shown, for the reaction of Mo 3(μ 3- 34S)(μ 2- 32S e- 34S a) 3Cl 6 2− with PPh 3, that it is the equatorial μ 2-S 2 sulfurs that are predominantly eliminated.