Department of Chemistry, University of Illinois, 600 South Mathews Avenue, Urbana, Illinois 61801, USA.
J Am Chem Soc. 2010 Aug 25;132(33):11458-60. doi: 10.1021/ja1053835.
Iridium(I) complexes of aromatic (PCP) and aliphatic (D(t)BPP) 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)(NHNC(5)H(10)), slowly undergoes a second N-H bond cleavage at the alpha-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.
芳基（PCP）和脂肪族（D(t)BPP）钳形配体的铱（I）配合物会使肼衍生物的 N-H 键单一断裂，形成腙配合物，并使两个 N-H 键同时断裂，形成罕见的晚期过渡金属氨基氮烯配合物。在某些情况下，还观察到肼中的 N-N 键的断裂。苯甲酮腙和 1-氨基哌啶的 N-H 键的氧化加成作用在几分钟内即可向铱（I）配合物中生成相应的氢铱（III）腙配合物。含有芳基钳形配体的配合物（PCP）Ir（H）（NHNC（5）H（10））缓慢地在α-N-H 键处进行第二次 N-H 键断裂，并消除氢，以高产率生成氨基氮烯配合物和氢气。含有芳基钳形配体的（PCP）Ir（I）片段与甲基取代的肼反应形成氨基氮烯配合物、异氰化物铱（III）二氢化物配合物和氨的混合物。后两种产物可能是通过甲基 C-H 键的初始氧化加成和随后的 N-N 键断裂形成的。氨基氮烯配合物与 CO 或可进行氧化加成的试剂（MeI 和 PhOH）的反应导致“异二嗪”片段的释放，生成叠氮化合物和四嗪衍生物。
