Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Oxidative addition of diphenyl disulfide across a Ta=Ta bond. Preparation and characterization of (TaCl/sub 3/(Me/sub 2/S))/sub 2/(. mu. -SPh)/sub 2/

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00223a012· OSTI ID:5908550
The tantalum complex (SMe/sub 2/)Cl/sub 2/Ta(..mu..-Cl)/sub 2/(..mu..-SMe/sub 2/)TaCl/sub 2/(SMe/sub 2/), possessing a sigma/sup 2/..pi../sup 2/ Ta=Ta double bond, reacts readily with PhSSPh to give (SMe/sub 2/)Cl/sub 3/Ta(..mu..-SPh)/sub 2/TaCl/sub 2/(SMe/sub 2/). In this reaction, the starting material loses the bridging SMe/sub 2/ ligand and two chloride bridges are broken while only two new SPh bridges are formed in the final product. This oxidative-addition reaction of the S-S single bond to the Ta=Ta double bond converts the face-sharing bioctahedron structure of the starting compound to an edge-sharing bioctahedron structure in the final dimer, with concomitant change of the oxidation state of tantalum from III to IV. The product is the first example of a d/sup 1/-d/sup 1/ ditantalum thiolate-bridged dimer. Important structural data for (SMe/sub 2/)Cl/sub 3/Ta(..mu..-SPh)/sub 2/TaCl/sub 3/(SMe/sub 2/), which has an inversion center, are determined. The new compound crystallizes in the monoclinic space group C2/c with a = 17.934 (5) A, b = 12.445 (4) A, c = 11.705 (4) A, ..beta.. = 92.50 (3)/sup 0/, V = 2610 (2) A/sup 3/, and Z = 4. Solid-state /sup 13/C NMR spectroscopy with cross polarization and magic-angle spinning (CP/MAS) at 28 and -103 /sup 0/C provides evidence that this compound is diamagnetic. 12 references, 3 figures, 4 tables.
Research Organization:
Texas A and M Univ., College Station
OSTI ID:
5908550
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:3; ISSN INOCA
Country of Publication:
United States
Language:
English