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 in | Dalton transactions : an international journal of inorganic chemistry Vol. 46; no. 22; pp. 7145 - 7149 |
|---|---|
| Main Authors | , , , , |
| Format | Journal Article |
| Language | English |
| Published |
England
06.06.2017
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| Subjects | |
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| Abstract | 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. |
|---|---|
| AbstractList | Thermal or photolytic activation of well-defined mononuclear [Co(N
3
)(PNP)] (PNP = 2,2′-bis(diisopropylphosphino)-4,4′-ditolylamido) results in the structurally characterized dinuclear species [Co(μ-N;κ
3
-
P
,
N
,
N
-PN
P
N)]
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(PN
P
N
H
)] (
4
) by protonation of the N-bridges. 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. 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. 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( mu -N; Kappa 3-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. |
| Author | Baij, L de Bruin, B Siegler, M A Vreeken, V van der Vlugt, J I |
| Author_xml | – sequence: 1 givenname: V surname: Vreeken fullname: Vreeken, V email: j.i.vandervlugt@uva.nl organization: Homogeneous, 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 – sequence: 2 givenname: L surname: Baij fullname: Baij, L – sequence: 3 givenname: B surname: de Bruin fullname: de Bruin, B – sequence: 4 givenname: M A surname: Siegler fullname: Siegler, M A – sequence: 5 givenname: J I surname: van der Vlugt fullname: van der Vlugt, J I |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/28517014$$D View this record in MEDLINE/PubMed |
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| Snippet | Thermal or photolytic activation of well-defined mononuclear [Co(N
)(PNP)] (PNP = 2,2'-bis(diisopropylphosphino)-4,4'-ditolylamido) results in the structurally... Thermal or photolytic activation of well-defined mononuclear [Co(N 3 )(PNP)] (PNP = 2,2′-bis(diisopropylphosphino)-4,4′-ditolylamido) results in the... Thermal or photolytic activation of well-defined mononuclear [Co(N3)(PNP)] (PNP = 2,2'-bis(diisopropylphosphino)-4,4'-ditolylamido) results in the structurally... |
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| SubjectTerms | Activation Bonding Cobalt Density functional theory Dimers Insertion Ligands Mathematical analysis |
| Title | N-Atom transfer via thermal or photolytic activation of a Co-azido complex with a PNP pincer ligand |
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