Oxygen Reduction Reactions of Monometallic Rhodium Hydride Complexes
收藏NIAID Data Ecosystem2026-03-07 收录
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https://figshare.com/articles/dataset/Oxygen_Reduction_Reactions_of_Monometallic_Rhodium_Hydride_Complexes/2509429
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资源简介：
Selective reduction of oxygen is mediated by a series
of monometallic
rhodium(III) hydride complexes. Oxidative addition of HCl to trans-RhICl(L)(PEt3)2 (1a, L = CO; 1b, L = 2,6-dimethylphenylisocyanide
(CNXy); 1c, L = 1-adamantylisocyanide (CNAd)) produces
the corresponding RhIII hydride complex cis-trans-RhIIICl2H(L)(PEt3)2 (2a–c). The
measured equilibrium constants for the HCl-addition reactions show
a pronounced dependence on the identity of the “L” ligand.
The hydride complexes effect the reduction of O2 to water
in the presence of HCl, generating trans-RhIIICl3(L)(PEt3)2 (3a–c) as the metal-containing product. In the case of 2a, smooth conversion to 3a proceeds without spectroscopic
evidence for an intermediate species. For 2b/c, an aqua
intermediate, cis-trans-[RhIII(OH2)Cl2(L)(PEt3)2]Cl (5b/c), forms along the pathway to producing 3b/c as the final products. The aqua complexes were independently
prepared by treating peroxo complexes trans-RhIIICl(L)(η2-O2)(PEt3)2 (4b/c) with HCl to rapidly produce a mixture
of 5b/c and 3b/c. The reactivity of the
peroxo species demonstrates that they are plausible intermediates
in the O2-reduction chemistry of hydride complexes 2a–c. These results together show that
monometallic rhodium hydride complexes are capable of promoting selective
reduction of oxygen to water and that this reaction may be controlled
with systematic alteration of the ancillary ligand set.
创建时间：
2016-02-20
