Communication

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

  1. Dr. Yann Gloaguen1,
  2. Christophe Rebreyend1,
  3. Dr. Martin Lutz4,
  4. Pravin Kumar3,
  5. Dr. Martina Huber3,
  6. Dr. Ir. Jarl Ivar van der Vlugt1,
  7. Prof. Dr. Sven Schneider2,* and
  8. Prof. Dr. Bas de Bruin1,*

Article first published online: 19 MAY 2014

DOI: 10.1002/anie.201403445

Issue

Angewandte Chemie International Edition

Angewandte Chemie International Edition

Volume 53, Issue 26, pages 6814–6818, June 23, 2014


Additional Information

How to Cite

Gloaguen, Y., Rebreyend, C., Lutz, M., Kumar, P., Huber, M., van der Vlugt, J. I., Schneider, S. and de Bruin, B. (2014), An Isolated Nitridyl Radical-Bridged {Rh(N.)Rh} Complex. Angew. Chem. Int. Ed., 53: 6814–6818. doi: 10.1002/anie.201403445

Author Information

  1. 1

    van‘t Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam (The Netherlands)

  2. 2

    Institut für Anorganische Chemie, Georg-August-Universität, Göttingen (Germany)

  3. 3

    Leiden Institute of Physics, Leiden University (The Netherlands)

  4. 4

    Crystal and Structural Chemistry, Bijvoet Center for Biomolecular Research, Utrecht University (The Netherlands)

* Sven Schneider, Institut für Anorganische Chemie, Georg-August-Universität, Göttingen (Germany)
Bas de Bruin, van‘t Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam (The Netherlands)

  1. †

    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.

Publication History

  1. Issue published online: 20 JUN 2014
  2. Article first published online: 19 MAY 2014
  3. Manuscript Received: 18 MAR 2014

Funded by

  • ERC. Grant Number: 202886
  • NWO-CW. Grant Number: 016.122.613
  • NWO-FOM. Grant Number: 10SMPA04
  • COST action CM1205

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Keywords:

  • EPR spectroscopy;
  • nitrogen donors;
  • non-innocent ligands;
  • radicals;
  • rhodium

Abstract

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[DOUBLE BOND]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.

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