Redox non-innocence of a nitrido bridge in a methane-activating dimer of iron phthalocyanine

被引：36

作者：

Silaghi-Dumitrescu, Radu ^{[1
]}

Makarov, Sergei V. ^{[2
]}

Uta, Matei-Maria ^{[1
]}

Dereven'kov, Ilia A. ^{[2
]}

Stuzhin, Pavel A. ^{[2
]}

机构：

[1] Univ Babes Bolyai, RO-400028 Cluj Napoca, Romania

[2] State Univ Chem & Technol, Ivanovo 153000, Russia

来源：

NEW JOURNAL OF CHEMISTRY | 2011年 / 35卷 / 05期

关键词：

ELECTRON-PARAMAGNETIC-RESONANCE; CYTOCHROME-P450; ENZYMES; THEORETICAL PERSPECTIVE; CATALYZES OXIDATION; PORPHYRIN DIMERS; HEME; DIOXYGEN; HEMOPROTEINS; MECHANISM; BENZENE;

D O I：

10.1039/c0nj00827c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A nitrido-bridged iron phthalocyanine has recently been shown to catalyze hydrocarbon activation, displaying in this respect distinctly different reactivity than the monomeric phthalocyanine or the oxo-bridged dimer. Here, DFT calculations are shown on models of this catalyst, indicating a distinct difference in electronic structures between the mu-oxo and mu-nitrido-bridged dimers, with the nitride acting as a remarkable charge reservoir and acquiring S = 1 N-character while the oxo bridge remains redox-inert; this difference in charge localization appears to be mirrored by a tendency towards higher symmetry in the Fe-N/O bonds with the nitrido bridge compared to the oxo one, and by a tendency of the nitride to favour lower-spin states more efficiently than the oxide.

引用

页码：1140 / 1145

页数：6

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