O-PROTONATION OF THE (MU-H)RU3(MU-CO)(CO)10 ANION - REARRANGEMENT OF (MU-H)RU3(MU-COH)(CO)10 TO H(MU-H)RU3(CO)11 - KINETICS OF REDUCTIVE ELIMINATION OF HYDROGEN FROM H(MU-H)RU3(CO)11

The kinetic product from protonation of [^-H)Ru3(m-CO)(CO)10]~ with CF3S03H is (^-H)Ru3(/i-COH)(CO)10. This product rearranges to H(m-H)Ru3(CO)n within 20 s at 25 °C. Alternatively, H(μ-H)Ru3(CO)u is the only product formed by protonation with CF3C02H. Products were characterized by *H NMR spectroscopy at low temperatures and by FT-IR spectroscopy at ambient temperature. H(μ-H)Ru3(CO)u is isostructural with the Os analogue, having one bridging and one terminal hydride ligand; these hydrides undergo exchange on the NMR time scale (AG* = 51.9 kJ/mol at 236 K). H^-H)Ru3(CO)ndecomposes rapidly (fc(298 K) = (1.27 ± 0. 19) χ 10-2 s-1) to Ru3(CO)12 and hydrogen. Activation parameters (AH* = 124 (6) kJ/mol, AS* = 136 (20) J/(K mol)) and the deuterium kinetic isotope effect (kH/kO= 1.12 (0.09) at 298 K) were determined by using stopped-flow FT-IR spectroscopy. © 1990, American Chemical Society. All rights reserved.