An isolated nitridyl radical-bridged {Rh(N.)Rh} complex

Yann Gloaguen; Christophe Rebreyend; Martin Lutz; Pravin Kumar; Martina Huber; Jarl Ivar Vandervlugt; Sven Schneider; Bas Debruin

doi:10.1002/anie.201403445

An isolated nitridyl radical-bridged {Rh(N^.)Rh} complex

Yann Gloaguen, Christophe Rebreyend, Martin Lutz, Pravin Kumar, Martina Huber, Jarl Ivar Vandervlugt, Sven Schneider^*, Bas Debruin

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

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 ( ^.N^2-) 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 (^.N^2-) 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.

Original language	English
Pages (from-to)	6814-6818
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	53
Issue number	26
DOIs	https://doi.org/10.1002/anie.201403445 https://doi.org/10.1002/ange.201403445
Publication status	Published - 23 Jun 2014

Keywords

EPR spectroscopy
nitrogen donors
non-innocent ligands
radicals
rhodium

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@article{59d3317caf3442699c72fe807d4cff2f,

title = "An isolated nitridyl radical-bridged {Rh(N.)Rh} complex",

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",

author = "Yann Gloaguen and Christophe Rebreyend and Martin Lutz and Pravin Kumar and Martina Huber and Vandervlugt, {Jarl Ivar} and Sven Schneider and Bas Debruin",

note = "Also published in: Angewandte Chemie volume 126, issue 26, 6932-6936 (2014)",

year = "2014",

month = jun,

day = "23",

doi = "10.1002/anie.201403445",

language = "English",

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pages = "6814--6818",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

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T1 - An isolated nitridyl radical-bridged {Rh(N.)Rh} complex

AU - Gloaguen, Yann

AU - Rebreyend, Christophe

AU - Lutz, Martin

AU - Kumar, Pravin

AU - Huber, Martina

AU - Vandervlugt, Jarl Ivar

AU - Schneider, Sven

AU - Debruin, Bas

N1 - Also published in: Angewandte Chemie volume 126, issue 26, 6932-6936 (2014)

PY - 2014/6/23

Y1 - 2014/6/23

N2 - 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.

AB - 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.

KW - EPR spectroscopy

KW - nitrogen donors

KW - non-innocent ligands

KW - radicals

KW - rhodium

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