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 04:00:00 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), Journal Name: Inorganic Chemistry; (United States) Vol. 32:24; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

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