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

Thermal or photolytic activation of well-defined mononuclear [Co(N )(PNP)] (PNP = 2,2'-bis(diisopropylphosphino)-4,4'-ditolylamido) results in the structurally characterized dinuclear species [Co(μ-N;κ -P,N,N-PN N)] (3), with two N-bridging phosphiniminato bridgeheads. Density Functional T...

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Published inDalton transactions : an international journal of inorganic chemistry Vol. 46; no. 22; pp. 7145 - 7149
Main Authors Vreeken, V, Baij, L, de Bruin, B, Siegler, M A, van der Vlugt, J I
Format Journal Article
LanguageEnglish
Published England 06.06.2017
Subjects
Activation
Bonding
Cobalt
Density functional theory
Dimers
Insertion
Ligands
Mathematical analysis
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Summary:Thermal or photolytic activation of well-defined mononuclear [Co(N )(PNP)] (PNP = 2,2'-bis(diisopropylphosphino)-4,4'-ditolylamido) results in the structurally characterized dinuclear species [Co(μ-N;κ -P,N,N-PN N)] (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(PN N )] (4) by protonation of the N-bridges.
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ISSN:1477-9226
1477-9234
DOI:10.1039/c7dt01712j