The Late Transition-Metal Nitride Complexes with High Oxidation-States: Synthesis and their Nitrogen-Atom Transfer Reactions

为了合成新的氮化铱(V)或氮化铱（III）配合物，研究了叠氮化铱（III）前体的光解反应。在（五甲基环戊二烯基）（叠氮）铱（III）配合物中，以2-吡啶硫代酸盐为共配体[Cp^*Ir(2-Spy)(N_3)]，来源于叠氮化物的氮原子被插入到Ir- n （py）键中，形成具有两足钢琴凳结构的五坐标配合物[Cp^*Ir(1-N-2-Spy)]。该配合物与碘化甲酯（作为亲电试剂）反应生成空气稳定的配合物，该配合物带有一种新的亚胺/硫酸酯型配体[Cp^*Ir(1-NMe-2-Spy)]I。结果表明，1-N-2-Spy^<2->和1-NMe-2-Spy^-两种配体均具有足够的π-构性，可以稳定五配位配合物中的配位不饱和Ir（III）中心。这些结果表明氮原子转移工艺可用于叠氮化物配合物光解合成含氮多的有机配体。为了寻找另一种类型的光化学反应性，制备了几种具有不同共配体的叠氮化铱配合物。其中，我们可以得到结构上非常有趣的复合物。例如，在1,8-萘嘧啶或苯并咪唑-2-硫酸盐的情况下，双核配合物的特征桥接结构已被x射线分析揭示。此外，当与2,2'-联吡啶或1,10-菲罗啉共配体的叠氮配合物被光分解时，通过溶剂乙腈在配位叠氮配体上的1,3-偶极环加成，得到了意想不到的由5-甲基四氮酸盐不对称桥接的双核配合物。综上所述，本研究开发了利用叠氮化铱配合物光解合成含氮有机化合物的新方法，形成新的氮化铱(V)或氮化铱（III）中间体，而配合物的氮原子转移过程将是这些反应的关键步骤。少

In order to synthesize novel iridium(V) nitride (or iridium(III) nitrenide) complexes which are expected to show interesting nitrogen-atom transfer reactions, photolysis of iridium(III) azide precursors have been examined. In the case of (pentamethylcyclopentadienyl)(azido)iridium(III) complex having a 2-pyridinethiolate as a co-ligand, [Cp^*Ir(2-Spy)(N_3)], a nitrogen-atom originated from the azide was inserted into the Ir-N(py) bond, affording a five-coordinate complex with a two-legged piano stool structure, [Cp^*Ir(1-N-2-Spy)]. This complex reacted with methyl iodide (as an electrophile) to give an air-stable complex bearing a new didentate imine/thiolate-type ligand, [Cp^*Ir(1-NMe-2-Spy)]I. It was found that both of the ligands, 1-N-2-Spy^<2-> and 1-NMe-2-Spy^-, have a sufficient π-donicity to stabilize a coordinatively unsaturated Ir(III) center in the five-coordinated complexes. These results are indicative of usability of nitrogen-atom transfer process for syntheses of nitrogen … More -containing organic ligands via photolysis of the azide complexes.Aiming to find another types of photochemical reactivity, several new iridium(III) azide complexes with various co-ligands have been prepared. Among them, we could obtain structurally very interesting complexes. For example, in the case of 1,8-naphthylidine or benzimidazole-2-thiolate, dinuclear complexes with characteristic bridging structures have been revealed by X-ray analyses. Furthermore, when the azido complexes with co- ligand of 2,2'-bipyridine or 1,10-phenanthroline were photolyzed, unexpected dinuclear complexes bridged asymmetrically by 5-methyltetrazolate were resulted via 1,3-dipolar cycloaddition of the solvent acetonitrile to the coordinated azide ligand.In summary, this study developed new synthetic methods for nitrogen-containing organic compounds by photolysis of iridium(III) azide complexes, in which novel iridium(V) nitride or iridium(III) nitrenide intermediates would be formed, and the nitrogen-atom transfer process from the complexes would be a key step in these reactions. Less