Miguel A. Esteruelas, A. Lledós, M. Oliván
Aug 8, 2003
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Influential Citations
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Journal
Organometallics
Abstract
Complex (1) reacts with acetophenone and benzophenone to give (R = CH3 (2), Ph (3)). In the solid state, the structure of 2 determined by X-ray diffraction analysis can be described as a pentagonal bipyramid with the phosphorus atoms of the phosphines occupying axial positions. In solution the hydride ligands of 2 and 3 undergo a thermally activated site exchange process. The activation parameters for the exchange are ΔH⧧ = 11.9 ± 0.5 kcal·mol-1 and ΔS⧧ = −0.7 ± 1.2 cal·mol-1·K-1 for 2 and ΔH⧧ = 11.8 ± 0.2 kcal·mol-1 and ΔS⧧ = −2.6 ± 1.9 cal·mol-1·K-1 for 3. The reaction of 1 with perdeuterated benzophenone affords the hydride-deuteride (3-d10), suggesting that the activation takes place on the monohydride intermediate OsH(SnPh2Cl)(PiPr3)2. The reaction pathway for the formation of this intermediate is evaluated by DFT calculations. Complex 1 also reacts with 2,3,4,5,6-pentafluorobenzophenone, 2-fluoroacetophenone, and benzophenone imine. The reactions with the partially fluorinated ketones give (4) and (...