Jump to main content
Jump to site search

Issue 39, 2017
Previous Article Next Article

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

Author affiliations

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 28 Apr 2017, accepted on 04 Jul 2017 and first published on 04 Jul 2017


Article type: Paper
DOI: 10.1039/C7DT01565H
Citation: Dalton Trans., 2017,46, 13273-13289
  •   Request permissions

    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

Search articles by author

Spotlight

Advertisements