Role of the Metal in the Bonding and Properties of Bimetallic Complexes Involving Manganese, Iron, and Cobalt

This poster (courtesy of Scientific Information Services, Advanced Photon Source), summarizing research that was a highlight in “APS Science 2014,” is on the APS exhibit in the Bldg. 401 Atrium at Argonne.

A multidentate ligand platform is introduced that enables the isolation of both homo- and heterobimetallic complexes of divalent first-row transition metal ions such as Mn(II), Fe(II), and Co(II). By means of a two-step metalation strategy, five bimetallic coordination complexes were synthesized with the general formula M₁M₂Cl(py₃tren), where py₃tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. The metal–metal pairings include dicobalt (1), cobalt–iron (2), cobalt–manganese (3), diiron (4), and iron–manganese (5). The bimetallic complexes have been investigated by X-ray diffraction and X-ray anomalous scattering studies, cyclic voltammetry, magnetometry, Mössbauer spectroscopy, UV–vis–NIR spectroscopy, NMR spectroscopy, combustion analyses, inductively coupled plasma optical emission spectrometry, and ab initio quantum chemical methods. Only the diiron chloride complex in this series contains a metal–metal single bond (2.29 Å). The others show weak metal–metal interactions (2.49 to 2.53 Å). The diiron complex is also distinct with a septet ground state, while the other bimetallic species have much lower spin states from S = 0 to S = 1. We propose that the diiron system has delocalized metal–metal bonding electrons, which seems to correlate with a short metal–metal bond and a higher spin state. Multiconfigurational wave function calculations revealed that, indeed, the metal–metal bonding orbitals in the diiron complex are much more delocalized than those of the dicobalt analogue.

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Stephen J. Tereniak †, Rebecca K. Carlson †‡, Laura J. Clouston †, Victor G. Young , Jr.†, Eckhard Bill *§, Rémi Maurice †‡, Yu-Sheng Chen ∥, Hyun Jung Kim †‡, Laura Gagliardi *†‡, and Connie C. Lu*†

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

^‡ Supercomputing Institute and Chemical Theory Center, University of Minnesota, Minneapolis, Minnesota 55455, United States

^§ Max Planck Institut für Chemische Energiekonversion, Stiftstraße 34-36, 45470 Mülheim an der Ruhr,Germany

^∥ ChemMatCARS, University of Chicago, Argonne, Illinois 60439, United States

J. Am. Chem. Soc., 2014, 136 (5), pp 1842–1855

DOI: 10.1021/ja409016w

http://pubs.acs.org/doi/full/10.1021/ja409016w