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2 H ‐Azirines as Ligands: Structural Characterization of the First Neutral and Cationic ( η 5 ‐C 5 Me 5 )Rh( III ) 2 H ‐Azirine Complexes
Author(s) -
Roedel J. Nicolas,
Lorenz IngoPeter
Publication year - 2008
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200800098
Subject(s) - azirine , rhodium , cationic polymerization , chemistry , stacking , metal , crystallography , molar ratio , stereochemistry , catalysis , polymer chemistry , organic chemistry , ring (chemistry)
The synthesis and structural characterization of two azirine rhodium( III ) complexes are described. The stabilization, N ‐coordination and phenylgroup π‐stacking of the highly reactive and strained 3‐phenyl‐2 H ‐azirine by transition metal coordination is observed. The reaction of the dimeric complex [( η 5 ‐C 5 Me 5 )RhCl 2 ] 2 with 3‐phenyl‐2 H ‐azirine (az) in CH 2 Cl 2 at room temperature in a 1:2 molar ratio afforded the neutral mono‐azirine complex [( η 5 ‐C 5 Me 5 )RhCl 2 (az)]. The subsequent reaction of [( η 5 ‐C 5 Me 5 )RhCl 2 ] 2 with six equivalents of az and 4 equivalents of AgOTf yielded the cationic tris‐azirine complex [( η 5 ‐C 5 Me 5 )Rh(az) 3 ](OTf) 2 . After purification, all complexes have been fully characterized. The molecular structures of the novel rhodium( III ) complexes exhibit slightly distorted octahedral coordination geometries around the metal atoms.