Reactions of phosphine-substituted alkylidyne carbonyltungsten complexes with dithiocarbamate ligands: Phosphine substitution and alkylidyne- carbonyl coupling

• Published in: Journal of organometallic chemistry Vol. 479; no. 1; pp. 47 - 53
• Main Authors: Mayr, Andreas, Chang, Richard T., Tsung-Yi, Lee, On, Ki Cheung, Kjelsberg, Michael A., McDermott, Gregory A., Van Engen, Donna
• Format: Journal Article
• Language: English
• Published: Lausanne Elsevier B.V 04.10.1994; Elsevier Science
• Subjects: Alkylidyne complexes; Chemistry; Condensed matter: structure, mechanical and thermal properties; Coupling reactions; Exact sciences and technology; Ketenyl; Organic chemistry; Organic compounds; Organometalloidal and organometallic compounds; Phosphines; Physics; Preparations and properties; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Transition metals derivatives; Tungsten; Ketenyl; Alkylidyne complexes; Coupling reactions; Tungsten; Phosphines; Pyrolysis; Ligand substitution; Tertiary phosphine; Molecular structure; Organic ligand; Metallocycle; Transition metal Carbonyl Complexes; Tungsten Organic compounds; Experimental study; X ray diffraction; Chemical coupling; Chloro complex; Ylidyne complex; Tungsten Carbonyl Complexes; Carbyne; Crystalline structure
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/0022-328X(94)84090-3

Reaction of the alkylidyne tungsten complexes cis- and trans- [W(CPh)Cl(CO) 2(PMe 3) 2] with sodium diethyldithiocarbamate affords the ketenyl complex [W(OCCPh)(S 2CNEt 2)(CO)(PMe 3) 2]. Reaction of [W(CPh)Cl(CO)(PMe 3) 3] with diethyldithiocarbamate gives the dithiocarbamate-substituted alkylidyne tungsten complex [W(CPh)(S 2CNEt 2)(CO)(PMe 3) 2]. Reaction of cis-[W(CPh)Cl(CO) 2(PPh 3) 2] with sodium dimethyldithiocarbamate leads to substitution of PPh 3 and formation of [W(CPh)(S 2CNMe 2)(CO) 2 (PPh 3)]. The solid state structure of [W(CPh)(S 2CNEt2)(CO)(PMe 3) 2] was determined by X-ray crystallography. Reaction of [W(CPh) (S 2CNEt 2)(CO)(Me 3) 2] with carbon monoxide in solution as well as in the solid state affords [W(OCCPh)( 2CNEt2)(CO)(PMe 3) 2]. Pyrolysis of [W(OCCPh)(S 2CNEt 2)(CO)(PMe 3) 2] at 100°C in toluene solution gives [W(CPh)(S 2CNEt 2)(CO)(PMe 3) 2].