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 indicates a predominant nitridyl radical ((·)N(2-)) character, which was confirmed computationally. Complex 3 reacts selectively with CO, producing two equivalents of [(PNN)Rh(I)(CO)] complex 4, presumably by nitridyl radical N,N-coupling.
van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam (The Netherlands).
Yann
Y
Gloaguen
Christophe
C
Rebreyend
Martin
M
Lutz
Pravin
P
Kumar
Martina
M
Huber
Jarl Ivar
JI
van der Vlugt
Sven
S
Schneider
Bas
B
de Bruin
D002248:Carbon Monoxide; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D008280:Magnetics; D008968:Molecular Conformation; D011725:Pyridines / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*
D056831:Coordination Complexes; D005609:Free Radicals; D011725:Pyridines; D007495:Iridium; D002248:Carbon Monoxide; D012238:Rhodium
EPR spectroscopy; nitrogen donors; non-innocent ligands; radicals; rhodium