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.

Sterically congested Lewis pairs cannot form Lewis adducts; instead they establish encounter complexes of "frustrated" Lewis pairs (FLPs). These encounter complexes have recently been recognized to be capable of activating, i.e., splitting, homopolar and polar single and double bonds, which rendered a new reactivity principle. With the help of qualitative orbital considerations this chapter reviews and explains the reactivity of FLPs toward homopolar Z-Z or Z-Z' single bonded molecules, such as H-H and C-H single bonds, assuming in the encounter complexes the action of strongly polarizing Coulombic fields originating from the FLP constituents. This reactivity principle has been extended in its view to the activating potential for homopolar Z-Z or Z-Z' single bonds of strongly polarized [X-Y ↔ X(+)-Y|(-)] σ and [X=Y ↔ X(+)-Y|(-)] π bonded molecules (X,Y = atoms or molecular fragments; electronegativity of X < electronegativity of Y). A striking analogy in the reaction behavior of FLPs and strongly polarized σ and π bonded molecules could be revealed based on the analyses of selected examples of "metal-free" (main group element reactions) or metal-based (containing transition metals) σ bond metathesis reactions and σ bond additions of H2 and alkanes to polarized main group element and metal to ligand π bonds. Related to the described polar reaction types are Z,Z' double atom or group transfers between highly polarized double bonds of XY and X'Y' molecules combining a Z,Z' elimination with an addition process. Multiple consecutive Z,Z' double atom or group transfers are denoted as double H transfer cascade reactions. Analyzed by examples are concerted or stepwise double H transfers and double H transfer cascades with Z,Z'=H,H from the "metal-free" and metal-based realms: the Meerwein- Pondorf-Verley reduction, H,H exchanges between amine boranes and between amine boranes and unsaturated organic compounds, and the crucial H,H transfer steps of Noyori's bifunctional and Shvo type transfer hydrogenation catalyses.