N-Atom transfer via thermal or photolytic activation of a Co-azido complex with a PNP pincer ligand
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Updated: Mar 2, 2026

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
V Vreeken1, L Baij, B de Bruin
1Homogeneous, Bioinspired and Supramolecular Group, van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, the Netherlands. j.i.vandervlugt@uva.nl.
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.
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