Dihydrogen Activation by Titanium Sulfide Complexes.

ABSTRACT: The titanocene sulfido complex Cp*(2)Ti(S)py (1, Cp* = pentamethylcyclopentadienyl; py = pyridine) is synthesized by addition of a suspension of S(8) to a toluene solution of Cp*(2)Ti-(CH(2)CH(2)) (2) and py. The rate of rotation of the pyridine ligand in solution was determined by (1)H NMR spectroscopy, and the structure of 1 was determined by X-ray crystallography. Complex 1 reacts reversibly with dihydrogen to give Cp*(2)Ti(H)SH (6) and py. Reaction of 1 with HD gives an equilibrium mixture of Cp*(2)Ti(D)SH and Cp*(2)Ti(H)SD; H(2) and D(2) are not formed in this reaction. 1D (1)H NMR magnetization transfer spectra and 2D EXSY (1)H NMR spectra of 6 in the presence of H(2) show that in solution the H(2), hydride, and hydrosulfido hydrogen atoms exchange. A four-center mechanism for this e

SUBMITTER: Sweeney ZK 

PROVIDER: S-EPMC1444909 | biostudies-literature | 1999 Dec

REPOSITORIES: biostudies-literature