期刊
DALTON TRANSACTIONS
卷 42, 期 24, 页码 8655-8666出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3dt50310k
关键词
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资金
- South African National Research Foundation
- Central Research Fund of the University of the Free State
- Norwegian Supercomputing Program (NOTUR) [NN4654K]
An experimental and computational chemistry study of the reactivity of [Rh(beta-diketonato)(CO)(P(OCH2)(3)CCH3)] complexes towards chemical and electrochemical oxidation shows that more electron withdrawing groups on the beta-diketonato ligand reduce electron density on the rhodium atom to a larger extent than electron donating groups. This leads to a slower second-order oxidative addition rate, k(1), and a higher electrochemical oxidation potential, E-pa(Rh), linearly related by ln k(1) = -11(1) E-pa(Rh) - 2.3(5). The reactivity of these complexes can be predicted by their DFT calculated HOMO energies: E-HOMO = -0.34(8)E-pa(Rh) - 5.04(4) = 0.032(5) ln k(1) - 4.96(4). k(1) of [Rh(beta-diketonato)(CO)(P(OCH2)(3)CCH3)] complexes is slower than that of related [Rh(beta-diketonato)(CO)(PPh3)] and [Rh(beta-diketonato)(P(OPh)(3))(2)] complexes due to the better pi-acceptor ability of the CO-phosphite-rhodium combination than that of CO-PPh3-rhodium or di-phosphite-rhodium.
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