Why is cobalt the best transition metal in transition-metal hangman corroles for O-O bond formation during water oxidation?

Wenzhen Lai*, Rui Cao, Geng Dong, Sason Shaik, Jiannian Yao, Hui Chen

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

88 Scopus citations

Abstract

O-O bond formation catalyzed by a variety of β-octafluoro hangman corrole metal complexes was investigated using density functional theory methods. Five transition metal elements, Co, Fe, Mn, Ru, and Ir, that are known to lead to water oxidation were examined. Our calculations clearly show that the formal Co V catalyst has a Co IV-corrole •+ character and is the most efficient water oxidant among all eight transition-metal complexes. The O-O bond formation barriers were found to change in the following order: Co(V) ≪ Fe(V) < Mn(V) < Ir(V) < Co(IV) < Ru(V) < Ir(IV) < Mn(IV). The efficiency of water oxidation is discussed by analysis of the O-O bond formation step. Thus, the global trend is determined by the ability of the ligand d-block to accept two electrons from the nascent OH -, as well as by the OH affinity of the TM(IV)=O species of the corresponding TM(V)=O·H 2O complex. Exchange-enhanced reactivity (EER) is responsible for the high catalytic activity of the Co(V) species in its S = 1 state.

Original languageEnglish
Pages (from-to)2315-2319
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume3
Issue number17
DOIs
StatePublished - 6 Sep 2012

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