An isolated nitridyl radical-bridged {Rh(N.)Rh} complex
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Publication date
2014-06-23
Authors
Gloaguen, Yann
Rebreyend, Christophe
Lutz, M.
Kumar, Pravin
Huber, Martina
Vandervlugt, Jarl Ivar
Schneider, Sven
Debruin, Bas
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Abstract
Photochemical activation of [(PNNH)Rh(N3)] (PNNH=6-di-(tert- butyl)phosphinomethyl-2,2′-bipyridine) complex2 produced the paramagnetic (S=1/2), [(PNN)Rh-N.-Rh(PNN)] complex3 (PNN-=methylene- deprotonated PNNH), which could be crystallographically characterized. Spectroscopic investigation of 3 indicates a predominant nitridyl radical ( .N2-) character, which was confirmed computationally. Complex3 reacts selectively with CO, producing twoequivalents of [(PNN)Rh I(CO)] complex4, 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 complex2. Complex2 reacts selectively with CO to produce complex3, presumably by N,N-coupling of nitridyl radicals.
Keywords
EPR spectroscopy, nitrogen donors, non-innocent ligands, radicals, rhodium, General Chemistry, Catalysis
Citation
Gloaguen, Y, Rebreyend, C, Lutz, M, Kumar, P, Huber, M, Vandervlugt, J I, Schneider, S & Debruin, B 2014, 'An isolated nitridyl radical-bridged {Rh(N.)Rh} complex', Angewandte Chemie - International Edition, vol. 53, no. 26, pp. 6814-6818. https://doi.org/10.1002/anie.201403445, https://doi.org/10.1002/ange.201403445