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N-Atom transfer via thermal or photolytic activation of a Co-azido complex with a PNP pincer ligand

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Abstract

Thermal or photolytic activation of well-defined mononuclear [Co(N3)(PNP)] (PNP = 2,2′-bis(diisopropylphosphino)-4,4′-ditolylamido) results in the structurally characterized dinuclear species [Co(μ-N;κ3-P,N,N-PNPN)]2 (3), with two N-bridging phosphiniminato bridgeheads. Density Functional Theory (DFT) calculations indicate the intermediacy of a mononuclear cobalt–nitrido complex, followed by N-migratory insertion into a Co–P bond. Reaction of 3 with two equiv. HCl leads to rupture of the dimer with formation of mononuclear [CoCl(PNPNH)] (4) by protonation of the N-bridges.

Graphical abstract: N-Atom transfer via thermal or photolytic activation of a Co-azido complex with a PNP pincer ligand

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Publication details

The article was received on 10 May 2017, accepted on 12 May 2017 and first published on 12 May 2017


Article type: Communication
DOI: 10.1039/C7DT01712J
Citation: Dalton Trans., 2017, Advance Article
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    N-Atom transfer via thermal or photolytic activation of a Co-azido complex with a PNP pincer ligand

    V. Vreeken, L. Baij, B. de Bruin, M. A. Siegler and J. I. van der Vlugt, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT01712J

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