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J Am Chem Soc. 2013 Sep 4;135(35):13142-8. doi: 10.1021/ja406506m. Epub 2013 Aug 23.

Systematic variation of metal-metal bond order in metal-chromium complexes.

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1
Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United States.

Abstract

In the field of metal-metal bonding, the occurrence of stable, multiple bonds between different transition metals is uncommon, and is largely unknown for different first-row metals. Adding to a recently reported iron-chromium complex, three additional M-Cr complexes have been isolated, where the iron site is systematically replaced with other first-row transition metals (Mn, Co, or Ni), while the chromium site is kept invariant. These complexes have been characterized by X-ray crystallography. The Mn-Cr complex has an ultrashort metal-metal bond distance of 1.82 Å, which is consistent with a quintuple bond. The M-Cr bond distances increases across the period from M = Mn to M = Ni, as the formal bond order decreases from 5 to 1. Theoretical calculations reveal that the M-Cr bonds become increasingly polarized across the period. We propose that these trends arise from increasing differences in the energies and/or contraction of the metals' d-orbitals (M vs Cr). The cyclic voltammograms of these heterobimetallic complexes show multiple one-electron transfer processes, from two to four redox events depending on the M-Cr pair.

PMID:
23901938
DOI:
10.1021/ja406506m
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