Metal-metal bonds involving vanadium atoms. A facile synthesis of a novel divanadium tetrakis(dithioacetate) that contains two .mu.-.eta.2-S2 bridges from bis(benzene)vanadium(0) and dithioacetic acid

Abstract

The diamagnetic title complex (III) crystallizes in P21/c with Z=2.

Structure of a binuclear disulfido–vanadium complex, [V2(μ-η2-S2)2(Et2NCS2)4]

“…The arrangement of the ligands is simply described as two distorted hexahedra that share a parallelogram and each has its other five faces strongly twisted. The bond distance of 2.884 (4),~ for V--V, which indicates a direct metal-metal interaction, is consistent with those of diamagnetic complexes (Duraj, Andras & Kibala, 1990;Halbert, Hutchings, Rhodes & Stiefel, 1986), and is much longer than the distance of 2.4 ,~ postulated for a d2--d 2 double bond . The average V--Sb (bridge) distance (2.409 ,~) is obviously shorter than the average value (2-503 A) for V--S, (terminal).…”

“…Although molecular vanadium dimers with $2 bridges are known, those with a Vz(/Z-~72-S2)2 core that have been hitherto structurally characterized are found in the mineral patronite (VS4)n, V2(/.~-T]2-52)2 -(BuENCS2)4 (Halbert, Hutchings, Rhodes & Stiefel, 1986) and V2(~-r/E-SE)E(S2CCH3)4 (Duraj, Andras & Kibala, 1990). …”

Facets of early transition metal–sulfur chemistry: Metal–sulfur ligand redox, induced internal electron transfer, and the reactions of metal–sulfur complexes with alkynes

“…A distinctly different synthetic procedure involving the reaction of V(g 6 -C 6 H 6 ) 2 with MeCS 2 H produces the V(IV) dimer, V 2 (l-S 2 ) 2 -(S 2 CMe) 4 [67]. Both these complexes exhibit structures closely related to those of the V 2 (l-S 2 ) 2 (S 2 CNR 2 ) 4 derivatives discussed above.…”

Redox reactions with bis(η6-arene) derivatives of early transition metals

“…The g 6 -arene derivatives of vanadium(0) were reported to react with alcohols such as ethylene glycol and glycerine, or with dithioacetic acid to afford vanadium(III) compounds of formula V(OR) 3 [19] or (CH 3 CS 2 ) 2 V(l-g 2 -S 2 ) 2 V(S 2 CCH 3 ) 2 [20], respectively. Oxidation to vanadium(II) occurs when V(g 6 -1,3,5-Me 3 C 6 H 3 ) 2 is reacted with CF 3 COOH in heptane or THF [1m] or with triphenylmethyl halides in DME [1l] (see Eqs.…”

“…Work up of the reaction mixture afforded [Cr(g 6 -MeC 6 H 5 ) 2 ][TiCl 4 (THF) 2 ], see Eq. (20), whose IR spectrum shows arene CH stretching at 3059 and 2982 cm À1 and two strong bands (1020-860 cm À1 ) due to coordinated THF. The compound was prepared also by reacting [Cr(g 6 -MeC 6 H 5 ) 2 ]Cl with TiCl 3 (THF) 3 (see Eq.…”