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Title: 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

Abstract

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 andmore » 2b. Compounds 1b, 2a[BF[sub 4]], and 3a have been characterized by X-ray crystallography. Crystals of 1b are orthorhombic.« less

Authors:
; ; ; ;  [1]; ; ;  [2]
  1. Universidad de Sevilla, CSIC (Spain) Instituto de Ciencia de Materialses, Serrano, Madrid (Spain)
  2. Universidad Complutense de Madrid (Spain)
Publication Date:
OSTI Identifier:
7242998
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (United States)
Additional Journal Information:
Journal Volume: 32:24; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
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

Citation Formats

Galindo, A, Pastor, A, Pizzano, A, Sanchez, L, Carmona, E, Gutierrez-Puebla, E, Monge, A, and Ruiz, C. 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. United States: N. p., 1993. Web. doi:10.1021/ic00076a025.
Galindo, A, Pastor, A, Pizzano, A, Sanchez, L, Carmona, E, Gutierrez-Puebla, E, Monge, A, & Ruiz, C. 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. United States. doi:10.1021/ic00076a025.
Galindo, A, Pastor, A, Pizzano, A, Sanchez, L, Carmona, E, Gutierrez-Puebla, E, Monge, A, and Ruiz, C. Wed . "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". United States. doi:10.1021/ic00076a025.
@article{osti_7242998,
title = {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},
author = {Galindo, A and Pastor, A and Pizzano, A and Sanchez, L and Carmona, E and Gutierrez-Puebla, E and Monge, A and Ruiz, C},
abstractNote = {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.},
doi = {10.1021/ic00076a025},
journal = {Inorganic Chemistry; (United States)},
issn = {0020-1669},
number = ,
volume = 32:24,
place = {United States},
year = {1993},
month = {11}
}