Bifunctional Rhenium Complexes for the Catalytic Transfer‐Hydrogenation Reactions of Ketones and Imines

The silyloxycyclopentadienyl hydride complexes [Re(H)(NO)(PR(3))(C(5)H(4)OSiMe(2)tBu)] (R=iPr (3 a), Cy (3 b)) were obtained by the reaction of [Re(H)(Br)(NO)(PR(3))(2)] (R=iPr, Cy) with Li[C(5)H(4)OSiMe(2)tBu]. The ligand-metal bifunctional rhenium catalysts [Re(H)(NO)(PR(3))(C(5)H(4)OH)] (R=iPr (5 a), Cy (5 b)) were prepared from compounds 3 a and 3 b by silyl deprotection with TBAF and subsequent acidification of the intermediate salts [Re(H)(NO)(PR(3))(C(5)H(4)O)][NBu(4)] (R=iPr (4 a), Cy (4 b)) with NH(4)Br. In nonpolar solvents, compounds 5 a and 5 b formed an equilibrium with the isomerized trans-dihydride cyclopentadienone species [Re(H)(2)(NO)(PR(3))(C(5)H(4)O)] (6 a,b). Deuterium-labeling studies of compounds 5 a and 5 b with D(2) and D(2)O showed H/D exchange at the H(Re) and H(O) positions. Compounds 5 a and 5 b were active catalysts in the transfer hydrogenation reactions of ketones and imines with 2-propanol as both the solvent and H(2) source. The mechanism of the transfer hydrogenation and isomerization reactions was supported by DFT calculations, which suggested a secondary-coordination-sphere mechanism for the transfer hydrogenation of ketones.