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Access to formally Ni(I) states in a heterobimetallic NiZn system

Uyeda, Christopher and Peters, Jonas C. (2012) Access to formally Ni(I) states in a heterobimetallic NiZn system. Chemical Science, 4 (1). pp. 157-163. ISSN 2041-6520. PMCID PMC4300139. doi:10.1039/c2sc21231e.

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Heterobimetallic NiZn complexes featuring metal centers in distinct coordination environments have been synthesized using diimine–dioxime ligands as binucleating scaffolds. A tetramethylfuran-containing ligand derivative enables a stable one-electron-reduced S = 1/2 species to be accessed using Cp_2Co as a chemical reductant. The resulting pseudo-square planar complex exhibits spectroscopic and crystallographic characteristics of a ligand-centered radical bound to a Ni(II) center. Upon coordination of a π-acidic ligand such as PPh_3, however, a five-coordinate Ni(I) metalloradical is formed. The electronic structures of these reduced species provide insight into the subtle effects of ligand structure on the potential and reversibility of the Ni^(II/I) couple for complexes of redox-active tetraazamacrocycles.

Item Type:Article
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URLURL TypeDescription DOIArticle CentralArticle
Uyeda, Christopher0000-0001-9396-915X
Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2012 The Royal Society of Chemistry. Received 10th August 2012. Accepted 10th September 2012. First published on the web 12 Sep 2012. This work was supported by the NSF Center for Chemical Innovation: Powering the Planet grant CHE-0802907, and by the Gordon and Betty Moore Foundation. We thank Larry Henling and Charlene Tsay for assistance with crystallography, Dr Angelo Di Bilio for EPR measurements, and Dr Limei Zhang and Dr Jens Kaiser for XAS measurements. We acknowledge the Gordon and Betty Moore Foundation, the Beckman Institute, and the Sanofi-Aventis BRP at Caltech for their generous support of the Molecular Observatory at Caltech. SSRL is operated for the DOE and supported by its Office of Biological and Environmental Research, and by the NIH, NIGMS (including P41GM103393) and the NCRR (P41RR001209).
Group:CCI Solar Fuels
Funding AgencyGrant Number
Gordon and Betty Moore FoundationUNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
Issue or Number:1
PubMed Central ID:PMC4300139
Record Number:CaltechAUTHORS:20130103-150617672
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:36156
Deposited By: Tony Diaz
Deposited On:07 Jan 2013 23:17
Last Modified:09 Nov 2021 23:20

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