%0 Journal Article %A Bakac, Andreja %A Guzei, Ilia A. %D 2000 %T Hydrogen Atom and Hydride Transfer in the Reactions of Chromium(IV) and Chromium(V) Complexes with Rhodium Hydrides. Crystal Structure of a Superoxorhodium(III) Product %U https://acs.figshare.com/articles/journal_contribution/Hydrogen_Atom_and_Hydride_Transfer_in_the_Reactions_of_Chromium_IV_and_Chromium_V_Complexes_with_Rhodium_Hydrides_Crystal_Structure_of_a_Superoxorhodium_III_Product/3626583 %R 10.1021/ic991098p.s002 %2 https://acs.figshare.com/ndownloader/files/5715327 %K hydride %K deuterium isotope effect %K rate constants %K L 1 %K solvate water molecules %K superoxo %K L 2 %K NH %K CH %K CN %K aneN %K Cr %K Chromium %K aq %K IV %K hydrogen atom abstraction %K Hydride %X The aquachromyl ion, CrIVaqO2+, reacts with the hydrides L(H2O)RhH2+ (L = L1 = [14]aneN4 and L2 = meso-Me6-[14]aneN4) in aqueous solutions in the presence of molecular oxygen to yield Craq3+ and the superoxo complexes L(H2O)RhOO2+. At 25 °C, the rate constants are ∼104 M-1 s-1 (L = L1) and 1.12 × 103 M-1 s-1 (L = L2). Both reactions exhibit a moderate deuterium isotope effect, kRhH/kRhD = ∼3 (L1) and 3.3 (L2), but no solvent isotope effect, kH2O/kD2O = 1. The proposed mechanism involves hydrogen atom abstraction followed by the capture of LRh(H2O)2+ with molecular oxygen. There is no evidence for the formation of L(H2O)Rh2+ in the reaction between L(H2O)RhH2+ and (salen)CrVO+. The proposed hydride transfer is supported by the magnitude of the rate constants (L = L1, k = 8800 M-1 s-1; (NH3)4, 2500; L2, 1000) and isotope effects (L = L1, kie = 5.4; L2, 6.2). The superoxo complex [L1(CH3CN)RhOO](CF3SO3)2·H2O crystallizes with discrete anions, cations, and solvate water molecules in the lattice. All moieties are linked by a network of hydrogen bonds of nine different types. The complex crystallized in the triclinic space group P1̄ with a = 9.4257(5) Å, b = 13.4119(7) Å, c = 13.6140(7) Å, α = 72.842(1)°, β = 82.082(1)°, γ = 75.414(1)°, V = 1587.69(14) Å3, and Z = 2. %I ACS Publications