N-H Activation of Hydrazines by Iridium(I). Double N-H Activation to Form Iridium Aminonitrene Complexes

Iridium(I) complexes of aromatic (PCP) and aliphatic (D^tBPP) pincer ligands undergo single cleavage of the N−H bonds of hydrazine derivatives to form hydrazido complexes and geminal double cleavage to form unusual late transition metal aminonitrene complexes. In some cases, the cleavage of the N−N bond in the hydrazine is also observed. Oxidative additions of the N−H bonds of benzophenone hydrazone and 1-aminopiperidine to iridium(I) complexes give the corresponding hydridoiridium(III) hydrazido complexes within minutes. The complex containing an aromatic pincer ligand, (PCP)Ir(H)(NHNC₅H₁₀), slowly undergoes a second N−H bond cleavage at the α-N−H bond and elimination of hydrogen to generate an aminonitrene complex and dihydrogen in high yield. The reactions of the (PCP)Ir(I) fragment containing an aromatic pincer ligand with methyl-substituted hydrazines form a mixture of aminonitrene complexes, isocyanide iridium(III) dihydride complexes, and ammonia. The latter two products are likely formed by initial oxidative addition of the methyl C−H bond and the subsequent N−N bond cleavage. Reactions of the aminonitrene complex with CO or reagents that undergo oxidative addition (MeI and PhOH) lead to release of the “isodiazine” fragment to give tetrazene and tetrazine derivatives. Read more on publisher's site.