Issue 37, 2014
From the journal:

Dalton Transactions

Assignment of the oxidation states of Zr and Co in a highly reactive heterobimetallic Zr/Co complex using X-ray absorption spectroscopy (XANES)†

Jeremy P. Krogman,a   James R. Gallagher,b   Guanghui Zhang, ORCID logo b   Adam S. Hock,bc   Jeffrey T. Miller*b  and  Christine M. Thomas*a  

* Corresponding authors

a Department of Chemistry, Brandeis University, 415 South Street MS 015, Waltham, Massachusetts 02453, USA
E-mail: thomasc@brandeis.edu

b Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439-4837, USA
E-mail: millerjt@anl.gov

c Department of Biological and Chemical Science, Illinois Institute of Technology, Chicago, Illinois 60647, USA

Abstract

The reduced heterobimetallic complex (THF)Zr(MesNPiPr2)3CoN2 (1) has been examined along with a series of structurally similar reference compounds using X-ray absorption near edge structure (XANES) spectroscopy. Complex 1 has been shown to be highly reactive, often via one-electron pathways that might be expected for a d1 ZrIII complex. However, the presence of two strongly interacting metals in complex 1 renders the assignment of oxidation states ambiguous. Both Zr and Co K-edge XANES spectra reveal that the most accurate description of complex 1 is that of a ZrIV/Co−I zwitterion. Electronic structure calculations support this assignment.

Graphical abstract: Assignment of the oxidation states of Zr and Co in a highly reactive heterobimetallic Zr/Co complex using X-ray absorption spectroscopy (XANES)

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Article information

DOI
https://doi.org/10.1039/C4DT01534G
Article type
Paper
Submitted
25 May 2014
Accepted
05 Aug 2014
First published
05 Aug 2014

Dalton Trans., 2014,43, 13852-13857

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Assignment of the oxidation states of Zr and Co in a highly reactive heterobimetallic Zr/Co complex using X-ray absorption spectroscopy (XANES)

J. P. Krogman, J. R. Gallagher, G. Zhang, A. S. Hock, J. T. Miller and C. M. Thomas, Dalton Trans., 2014, 43, 13852 DOI: 10.1039/C4DT01534G

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