An Isolated Nitridyl Radical-Bridged {Rh(N.)Rh} Complex

Photochemical activation of [(PNNH)Rh(N3)] (PNNH=6‐di‐(tert‐butyl)phosphinomethyl‐2,2′‐bipyridine) complex 2 produced the paramagnetic (S=1/2), [(PNN)RhN.‐Rh(PNN)] complex 3 (PNN−=methylene‐deprotonated PNNH), which could be crystallographically characterized. Spectroscopic investigation of 3 indic...

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Veröffentlicht in:Angewandte Chemie International Edition Jg. 53; H. 26; S. 6814 - 6818
Hauptverfasser: Gloaguen, Yann, Rebreyend, Christophe, Lutz, Martin, Kumar, Pravin, Huber, Martina, van der Vlugt, Jarl Ivar, Schneider, Sven, de Bruin, Bas
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Weinheim WILEY-VCH Verlag 23.06.2014
WILEY‐VCH Verlag
Wiley Subscription Services, Inc
Ausgabe:International ed. in English
Schlagworte:
Activation
Carbon Monoxide
Computation
Coordination Complexes - chemistry
Crystallography
Crystallography, X-Ray
Electron Spin Resonance Spectroscopy
EPR spectroscopy
Free Radicals - chemistry
Humidity
Iridium - chemistry
Magnetics
Molecular Conformation
nitrogen donors
non-innocent ligands
Photochemical
Photochemicals
Pyridines - chemistry
Radicals
rhodium
Rhodium - chemistry
Spectroscopy
radicals
non-innocent ligands
EPR spectroscopy
nitrogen donors
rhodium
ISSN:1433-7851, 1521-3773, 1521-3773
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Zusammenfassung:Photochemical activation of [(PNNH)Rh(N3)] (PNNH=6‐di‐(tert‐butyl)phosphinomethyl‐2,2′‐bipyridine) complex 2 produced the paramagnetic (S=1/2), [(PNN)RhN.‐Rh(PNN)] complex 3 (PNN−=methylene‐deprotonated PNNH), which could be crystallographically characterized. Spectroscopic investigation of 3 indicates a predominant nitridyl radical (.N2−) character, which was confirmed computationally. Complex 3 reacts selectively with CO, producing two equivalents of [(PNN)RhI(CO)] complex 4, presumably by nitridyl radical N,N‐coupling. The first isolated nitridyl radical (.N2−) complex was obtained by photochemical activation of the rhodium–azide complex [(PNNH)Rh(N3)] (1), producing N2, H2, and the paramagnetic complex 2. Complex 2 reacts selectively with CO to produce complex 3, presumably by N,N‐coupling of nitridyl radicals.
Bibliographie:NWO-CW - No. 016.122.613
ark:/67375/WNG-NV4JF42M-P
istex:DBAD5CDDF3782E95AD5CA9D9F52900F586B07A3B
COST action CM1205
ERC - No. 202886
NWO-FOM - No. 10SMPA04
Financial support by the ERC (grant number 202886, B.d.B.), NWO-CW (VICI grant number 016.122.613, B.d.B.), NWO-FOM (grant number 10SMPA04, M.H.), DFG (Emmy-Noether program grant SCHN950/2-1, S.S.), and COST action CM1205 (CARISMA) is gratefully acknowledged.
ArticleID:ANIE201403445
Financial support by the ERC (grant number 202886, B.d.B.), NWO‐CW (VICI grant number 016.122.613, B.d.B.), NWO‐FOM (grant number 10SMPA04, M.H.), DFG (Emmy‐Noether program grant SCHN950/2‐1, S.S.), and COST action CM1205 (CARISMA) is gratefully acknowledged.
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SourceType-Scholarly Journals-1
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.201403445