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Characterizations of novel binuclear transition metal polynitrogen compounds: M_2(N_5)_4 (M=Co, Rh and Ir)

机译:新型双核过渡金属聚硝化合物的特征:M_2(N_5)_4(M = CO,RH和IR)

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Theoretical studies on a series of binuclear transition metal pentazolides M_2(N_5)_4 (M=Co, Rh and Ir) predict Paddlewheel-type structures with very short metal-metal distances suggesting high-order metal-metal multiple bonds. Natural Bonding Orbital (NBO) analysis have indicated that the bonding between the metal atom and the five-membered ring is predominantly ionic for each M_2(N_5)_4 species, and a high-order metal-metal multiple bonding exists between the two metal atoms, in addition, the presence of the delocalized π orbital plays an important role in the stabilization of this metal-polynitrogen species. Nucleus independent chemical shift (NICS) values confirm that the planar N_5-exhibits aromaticity in these M_2(N_5)_4 species. The values of NICS(0.0), NICS(0.5) and NICS(1.0) for Co_2(N_5)_4 are larger than those of the other two M_2(N_5)_4 species (M=Rh and Ir), with the order of Co_2(N_5)_4>Rh_2(N_5)_4>Ir_2(N_5)_4. The dissociation energies into Mononuclear Fragments for M_2(N_5)_4 (M=Co, Rh and Ir) are predicted to be 82.9 (85.7), 139.9 (113.2), and 155.1 (149.7) kcal/mol, respectively. However, the dissociation energies for the loss of one pentazolato group from the M_2(N_5)_4 analysis have indicated that the Co_2(N_5)_4 is relatively higher at ~40 kcal/mol. Thermochemistry suggests Co_2(N_5)_4 to be a viable species.
机译:关于一系列双核过渡金属戊唑啉酯M_2(N_5)_4(M = CO,RH和IR)的理论研究预测了具有非常短的金属 - 金属距离的桨轮型结构,提出了高阶金属 - 金属多键。本质键合轨道(NBO)分析表明,金属原子和五元环之间的键合主要是针对每个M_2(N_5)_4种的离子,并且在两个金属原子之间存在高阶金属 - 金属多键另外,临床化π轨道的存在在该金属 - 多硝基物质的稳定中起着重要作用。核独立化学换档(NIC)值证实平面N_5-在这些M_2(N_5)_4种中表现出芳香性。用于CO_2(N_5)_4的NIC(0.0),NIC(0.5)和NIC(1.0)的值大于其他两个M_2(N_5)_4种(M = RH和IR),订单为CO_2 (n_5)_4> rh_2(n_5)_4> ir_2(n_5)_4。将解离能为M_2(N_5)_4(M = CO,RH和IR)的单核片段预测为82.9(85.7),139.9(113.2)和155.1(149.7)kcal / mol。然而,从M_2(N_5)_4分析中,用于丧失一种戊唑唑酸盐基团的解离能表明,CO_2(N_5)_4在〜40kcal / mol中相对较高。 Thermochemistry表明Co_2(N_5)_4是一种可行的物种。

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