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Issue 5, 2018
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Preparation and reactivity of a square-planar PNP cobalt(II)–hydrido complex: isolation of the first {Co–NO}8–hydride

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Abstract

The synthesis of a square-planar cobalt(II) hydrido complex supported by a pyrrole-based PNP ligand has been reinvestigated and its reactivity with various small molecules examined. Preparation of the complex was accomplished by treatment of the corresponding chloride complex, [CoCl(tBuPNP)] (tBuPNP = anion of 2,5-bis((di-tert-butylphosphino)methyl)pyrrole), with di-iso-butylaluminum hydride (DIBAL). Reaction of [CoCl(tBuPNP)] with other hydride sources such as NaEt3BH and LiAlH4 resulted in mixtures of the desired Co(II) hydride along with the reduced Co(I) species, [Co(N2)(tBuPNP)], as the primary product. The hydride complex exhibits facile migratory insertion chemistry with CO2 producing the corresponding Co(II) formate complex. When the Co–H complex is reacted with nitric oxide, the first example of a cobalt nitrosyl hydride complex is produced.

Graphical abstract: Preparation and reactivity of a square-planar PNP cobalt(ii)–hydrido complex: isolation of the first {Co–NO}8–hydride

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Publication details

The article was received on 17 Nov 2017, accepted on 11 Dec 2017 and first published on 12 Dec 2017


Article type: Paper
DOI: 10.1039/C7DT04339B
Citation: Dalton Trans., 2018,47, 1435-1441
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    Preparation and reactivity of a square-planar PNP cobalt(II)–hydrido complex: isolation of the first {Co–NO}8–hydride

    V. M. Krishnan, H. D. Arman and Z. J. Tonzetich, Dalton Trans., 2018, 47, 1435
    DOI: 10.1039/C7DT04339B

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