Molybdenum and tungsten complexes of S[sub 2]CPMe[sub 3] and related ligands. Crystal and molecular structures of W([eta][sup 3]-S[sub 2]CPMe[sub 3])(CO)[sub 2](PMe[sub 3])[sub 2], [Mo([eta][sup 2]-S[sub 2]C(H)PMe[sub 3])(CO)[sub 2](PMe[sub 3])[sub 2]]BF[sub 4], and [Mo([eta][sup 3]-SC(SMe)PMe[sub 3])(CO)[sub 2](PMe[sub 3])[sub 2]]I

Journal Article · Wed Nov 24 00:00:00 EST 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00076a025· OSTI ID:7242998

Galindo, A; Pastor, A; Pizzano, A; Sanchez, L; Carmona, E ^[1]; Gutierrez-Puebla, E; Monge, A; Ruiz, C ^[2]

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1. Universidad de Sevilla, CSIC (Spain) Instituto de Ciencia de Materialses, Serrano, Madrid (Spain)
2. Universidad Complutense de Madrid (Spain)

The known compound Mo(S[sub 2]CPMe[sub 3])(CO)[sub 2](PMe[sub 3])[sub 2] (1a) and the newly prepared tungsten analog W(S[sub 2]CPMe[sub 3])-(CO)[sub 2](PMe[sub 3])[sub 2] (1b), obtained by HCl elimination from WH(Cl)(CO)[sub 2](PMe[sub 3])[sub 3] upon treatment with CS[sub 2] and PMe[sub 3], contain a trihapto-bonded S,S[prime],C-trimethylphosphonium dithiocarboxylate ligand as demonstrated by X-ray studies carried out with 1b. Interaction of compounds 1 with protic acids affords the dithioformate species [M([eta][sup 2]-S[sub 2]C-(H)PMe[sub 3])(CO)[sub 2](PMe[sub 3])[sub 2]][sup +] (M = Mo (2a), W (2b)) while alkyl-derived electrophiles X[sup +] (X = Me, Et) furnish the cationic complexes [M[eta][sup 3]-SC(SR)PMe[sub 3](CO)[sub 2](PMe[sub 3])[sub 2]][sup +] (isolated in the form of iodide salts; M = Mo, R = Me (3a), R = Et (4); M = W, R = Me (3b)). These contain unprecedented S-alkyl phosphonio dithioester ligands as a result of alkylation at one of the sulfur atoms. The protonation reactions are proposed to occur by initial attack of H[sup +] at the strongly basic metal center followed by hydride migration to the electrophilic carbon atom. In accord with this, the reaction of the hydrides MH(Cl)(CO)[sub 2](PMe[sub 3])[sub 3] (M = Mo, W) with CS[sub 2] gives, under appropriate conditions, the cationic species 2a and 2b. Compounds 1b, 2a[BF[sub 4]], and 3a have been characterized by X-ray crystallography. Crystals of 1b are orthorhombic.

• OSTI ID: 7242998
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:24; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
MOLYBDENUM COMPLEXES
MOLECULAR STRUCTURE
TUNGSTEN COMPLEXES
CATIONS
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
ORTHORHOMBIC LATTICES
PHOSPHINES
X-RAY DIFFRACTION
CHARGED PARTICLES
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
DIFFRACTION
IONS
PHOSPHORUS COMPOUNDS
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties