81230-40-2Relevant 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 (2008/10/08)
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.
