The crystal structure of di-µ-ethanethiolato-µ-sulphido-bis[dichloro-(tetrahydrothiophen)tungsten(IV)(W–W)]: a confacial bioctahedral complex with a tungsten-to-tungsten bond

Abstract

The complex [(C,H,S)CI,W(p-S) (p-SEt),WCI,(SC,H,)] has been prepared by reaction of [WCI,(C,H,S),] with one mole equivalent of SiMe,(SEt) in CH,CI, solution. A single-crystal X-ray diffraction study shows that the molecule has a confacial bioctahedral structure with a W-W bond length of 2.524(1) A. The structure has been solved by heavy-atom methods from automated diffractometer data, and refined to R 0.025 (R' 0.037) for 1 593 reflections. The complex crystallizes in the orthorhombic system, space group Pnam, with a = 10.592(3), b = 12.618(4), c = 17.430(6) A, and Z = 4.

Confacial bioctahedral complexes of tungsten(IV) containing tungsten-to-tungsten bonds: X-ray crystal structures of di-μ-ethanethiolato-μ-sulfidobis[dichloro(dimethyl sulfide)-tungsten(IV) (W—W)] and tetraphenylphosphonium di-μ-ethane thiolato-μ-sulfido- bis[trichlorotungstate(IV) (W—W)]

“…The implication of this observation ture severely distorted by a strong metal-metal is that the interaction is indeed due to a direct interaction. metal-metal double bond, as was previously sugThere are two differences, however, in the gested (2). The distance is almost identical to that geometry of the three W(p-S)(p-SEt),W moieties.…”

“…Une Ctude par diffraction de rayons X sur un monocristal montre que cette molCcule a une structure bioctakdrique concafaciale avec une longueur de liaison de 2,52(2) A. On a rCsolu la structure par la mCthode des atomes Examples of tungsten(1V) complexes with well-(C~HSS)I, 3 (2). The starting material, WCI4(MezS)2?…”

C—S Bond-Breaking and Bond-Making Reactions in Molybdenum and Tungsten Complexes

“…Hence, by replacing CI by RS ligands in a high oxidation state Mo or W complex, reductive elimination of R 2 S 2 will leave coordinatively unsaturated metal centers in intermediate oxidation states, which are ideal precursors for cluster formation. This procedure proved to be a fruitful method for synthesizing binuclear complexes of W(IV), and, in some cases, mixed valent W(IV)/W(III) products were isolated (3)(4)(5)(6). Even in these reactions the dealkylation of thiolate ligands to give sulfido complexes is frequently observed, and the products from such reactions are extremely unpredictable.…”

“…This suggested an intermediate oxidation state of Mo or W, which of course would also be consistent with the +4 oxidation in an MS 2 phase. This limited the choice somewhat, and led to successful reactions between Cp 2 ZrH 2 and Mo(S l Bu) 4 , and Cp 2 NbH 3 and Mo(S l Bu) 4 respectively. The initial reaction was carried out with Cp 2 ZrH 2 , and Mo(S l Bu) 4 with benzene as solvent (72).…”

The crystal and molecular structure of di-μ-phenylthiolatobis[trichloro(dimethyl sulfide) tungsten(IV) (W—W)]

“…1). Recent studies in our laboratory have shown that the W-SR group in complexes of tungsten(1V) is unstable as a terminal entity (2)(3)(4)(5). By metathesis of WC14L, (L = Me2S; C4H8S) with SiMe3(SR) (R = alkyl, aryl), the intermediates WC4-,(SR),,L2, 2, have been prepared via the equation: \ 2 can undergo degradation by one of two observed pathways, depending on the stoichiometry (i.e.…”