Iridium , dinitrogen complexes

Tellers DM, Bergman RG. C—H bond activation by a rare cationic iridium dinitrogen complex. An important electronic effect in the chemistry of the hydridotris(pyrazolyl) borate ligand. /Am Chem Soc. 2000 122 954-955. 

Intramolecular C-N bond coupling in arylazides via C-H bond activation catalyzed by [Ir(COD)(OMe)]2 was recently reported [131]. The intermediate iridium nitrenoid complex (50) formed after the extrusion of dinitrogen is proposed as a reactive species, which can cleave the benzylic C-H bond to yield indoline derivatives (31). 

There are no new data on iridium dinitrogen species, or on dinitrogen complexes of Ni, Pd, or Pt. 

The olefin complexes of iron, nickel, rhodium, and iridium described in this chapter have found broad application in the synthesis of phosphine, phosphite, and carbonyl derivatives of these metals. In Chapter Two, the synthesis of another labile olefin complex, (ethylene)bis(tricyclohexylphosphine)nickel, is described as an initial step in synthesis of a complex of dinitrogen. 

Until today, it is a general rule that 1 1 adducts of diazoalkanes with transition metals are unstable in most cases. The stability can be significantly increased if dibenzoyldiazomethane is used as ligand. This was demonstrated by Cowie et al. (1986 a) in the synthesis of iridium complexes. As shown in (10-20), dibenzoyldiazomethane replaces the dinitrogen ligand in the starting material. The reaction is run... 

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