%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