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Issue 39, 2017
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A cobalt–nitrosyl complex with a hindered hydrotris(pyrazolyl)borate coligand: detailed electronic structure, and reactivity towards dioxygen

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Abstract

The cobalt–nitrosyl complex [Co(NO)(L3)] is supported by a highly hindered tridentate nitrogen ligand, hydrotris(3-tertiary butyl-5-isopropyl-1-pyrazolyl)borate (denoted as L3), and shows a linear Co–N–O unit. This complex was prepared by the reaction of the potassium salt of L3 with the cobalt–nitrosyl precursor [Co(NO)2(tmeda)](BPh4) (tmeda = N,N,N,′N′-tetramethylethylenediamine). The obtained cobalt–nitrosyl complex as well as the corresponding products from the reaction with dioxygen, [Co(η2-O2N)(L3)] and [Co(η2-O2NO)(L3)], were characterised by X-ray crystallography and a number of spectroscopic methods including IR/far-IR, UV-Vis, and NMR spectroscopy. We also performed MCD measurements and DFT calculations to further elucidate the electronic structure of [Co(NO)(L3)] and the optical properties of the complex. The MCD spectra reveal two NO-to-Co charge-transfer transitions with strong excited state displacements that give rise to vibrational progressions in the MCD spectra, indicative of a very covalent Co–NO bond. These results provide new insight into the properties of the Co–NO bond and the electron distribution in the complex, which is best described as [CoII(NO)(L3)].

Graphical abstract: A cobalt–nitrosyl complex with a hindered hydrotris(pyrazolyl)borate coligand: detailed electronic structure, and reactivity towards dioxygen

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Article information


Submitted
28 Apr 2017
Accepted
04 Jul 2017
First published
04 Jul 2017

Dalton Trans., 2017,46, 13273-13289
Article type
Paper

A cobalt–nitrosyl complex with a hindered hydrotris(pyrazolyl)borate coligand: detailed electronic structure, and reactivity towards dioxygen

K. Fujisawa, S. Soma, H. Kurihara, H. T. Dong, M. Bilodeau and N. Lehnert, Dalton Trans., 2017, 46, 13273
DOI: 10.1039/C7DT01565H

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