81230-35-5Relevant academic research and scientific papers
Kinetic and mechanistic studies on the reaction of (trithioperoxybenzoato)(dithiobenzoato)oxomolybdenum(IV), MoO(S3CC6H5)(S2CC6H 5), with tertiary phosphines
Tanaka, Koji,Kondo, Kazushi,Tanaka, Toshio
, p. 2483 - 2487 (1982)
Kinetics of the reaction of (trithioperoxybenzoato)(dithiobenzoato)oxomolybdenum(IV), MoO(S3CC6H5)(S2CC6H 5), with tertiary phosphine, R3P (R = H-Bu, C6H5), was investigated in 1,2-dichloroethane by the use of a stopped-flow spectrophotometer under pseudo-first-order conditions with excess R3P. The result has revealed that MoO(S3CC6H5)(S2CC6H 5) undergoes sulfur abstraction by n-Bu3P to give MoO(S2CC6H5)2, which further reacts with excess Bu3P, affording an intermediate involving the charge-transfer interaction between the S2CC6H5 moiety and n-Bu3P. The subsequent rearrangement of the intermediate proceeds in a zero-order kinetics with respect to the phosphine concentration, yielding cis-MoO(S2CC6H5)2(n-Bu 3P). The intermediate is stable below -40°C, and the structure is proposed on the basis of 13C and 1H NMR spectra. A similar sulfur abstraction from the S3CC6H5 moiety by Ph3P occurs. The subsequent reaction of MoO(S2CC6H5)2 with excess Ph3P, however, gives no charge-transfer complex between the S2CC6H5 moiety and Ph3P but an equilibrium mixture of trans- and cis-MoO(S2CC6H5)2(Ph3P) and the dissociated species in solution. The difference in mechanisms between the reactions of Ph3P and n-Bu3P toward MoO(S2CC6H5)2 is interpreted in terms of the donor properties of these phosphines.
Synthesis, Spectroscopy, and X-Ray Crystallographic Analysis of (η3-Dithiobenzoato-SCS')oxo(trithioperoxybenzoato-S,S',S'')molybdenum(IV) and μ-Oxo-bis
Tatsumisago, Masahiro,Matsubayashi, Gen-etsu,Tanaka, Toshio,Nishigaki, Satoshi,Nakatsu, Kazumi
, p. 121 - 128 (2007/10/02)
The title oxomolybdenum complexes IVO(S2CPh)(S3CPh)> and V2O3(S2CPh)4> have been obtained by the reaction of Na2 with in an acidic aqueous medium, followed by chromatographic separation on a silica column using carbon disulphide as eluant.They have been characterized by elemental analysis, i.r. and electronic spectroscopy.A single-crystal X-ray structure analysis of reveals a structure in which two MoVO(S2CPh)2 moieties are oxo-bridged.The monoclinic crystal, space group C2/c, has cell dimensions a = 38.951(9), b = 10.678(4), c = 16.777(3) Angstroem, β =111.28(1) deg, and Z=8.Block-diagonal least-squares refinement, based on 2340 independent reflections with /F/>3?(F), yields an R factor of 0.070.An X-ray structure analysis of has shown the presence of η3-dithiobenzoato- and trithioperoxybenzoato-ligands co-ordinated to oxomolybdenum(IV).The crystals are monoclinic, space group P21/c, with cell dimensions a = 15.614(2), b = 8.441(1), c = 13.125(2) Angstroem, β = 104.46(1) deg, and Z = 4.Least-squares refinement, based on 3767 independent reflections with /F/>3?(F), yields an R factor of 0.035.
