Issue 39, 2017

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

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

Supplementary files

Article information

Article type
Paper
Submitted
28 apr. 2017
Accepted
04 júl. 2017
First published
04 júl. 2017

Dalton Trans., 2017,46, 13273-13289

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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