A new molybdenum-tungsten-sulphur cluster complex family, [{(OC) 4M} xM′S 4] 2− (M = Mo or W, M′ = Mo or W; x = 1,2). Synthesis, structure and properties of a new trinuclear mixed-valence MoS cluster, [Et 4N] 2[(OC) 4MoS 2MoS 2Mo(CO) 4]

• Published in: Polyhedron Vol. 13; no. 1; pp. 125 - 131
• Main Authors: Zhuang, Botao, Yu, Pheihua, Huang, Liangren, He, Lingjie, Lu, Jiaxi
• Format: Journal Article
• Language: English
• Published: Oxford Elsevier Ltd 1994; New York, NY Elsevier Science
• Subjects: Carbonyl and nitrosyl compounds, and their complexes; Carbonyl and nitrosyl metals; Chemistry; Condensed matter: structure, mechanical and thermal properties; Exact sciences and technology; Inorganic chemistry and origins of life; Inorganic compounds; Physics; Preparations and properties; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Thio complex; Mixed oxidation number; Molecular structure; Trinuclear complex; Organic ligand; Complex cluster; Transition metal Carbonyl Complexes; Anionic complex; Zerovalent metal Complexes; Experimental study; X ray diffraction; Quaternary ammonium compound; Molybdenum Carbonyl Complexes; Cyclic voltammetry; Electrochemical properties; NMR spectrum; Tungsten Carbonyl Complexes; Crystalline structure
• ISSN: 0277-5387
• DOI: 10.1016/S0277-5387(00)86648-6

The reaction of molybdenum(0) dithiocarbamato carbonyl complexes, [Et 4N][Mo(CO) 4(S 2CNEt 2] with tetraethyl ammonium tetrathiomolybdate in MeOH affords a trinuclear mixed-valence MoS complex, [Et 4N] 2[(OC) 4MoS 2MoS 2Mo(CO) 4] ( 1) in high yield. The structure of 1 was studied by X-ray crystallography. The structure of the anion of 1 comprises two octahedra around low-valence molybdenum atoms and a tetrahedron with the high-valence molybdenum atom in the centre sharing two edges which are the line between the bridging sulphur atoms. Thus, 1 contains a trimetallic MoS 2MoS 2Mo core with two Mo 2S 2 planes sharing a molybdenum atom perpendicularly. The MoMo bond distances are 2.9979(6) and 3.0003(6) Å; the MoMoMo angle is 174.46(2)° and MoS bond lengths are 2.22 and 2.53 Å 95Mo NMR measurements show that the three molybdenum atoms in 1 are in two oxidation states. The cyclic voltammetry studies on 1 and the dinuclear complex, [(OC) 4MoS 2MoS 2] 2−, reveal the existence of two different redox metal centres in 1. The electron delocalization between the three mixed-valence molybdenum atoms is discussed by comparing them with the dinuclear molybdenum member of this cluster family.