A combined theoretical and experimental study of simple terminal group 6 nitride and phosphide N[triple bond]MX3 and P[triple bond]MX3 molecules.
A combined theoretical and experimental study of simple terminal group 6 nitride and phosphide N[triple bond]MX3 and P[triple bond]MX3 molecules.
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DOI：
10.1021/jp804469a
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发表时间：
2008-08
期刊：
影响因子：
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通讯作者：
Xuefeng Wang;L. Andrews;R. Lindh;V. Veryazov;B. Roos
中科院分区：
文献类型：
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作者：
Xuefeng Wang;L. Andrews;R. Lindh;V. Veryazov;B. Roos
含有末端金属氮化物和磷化物的有机金属配合物是重要的合成试剂。激光烧蚀的第 6 族金属原子与 NF 3、PF 3 和 PCl 3 反应，在插入和卤素转移后形成简单的最低能量 N[三键]MF 3 和 P[三键]MX 3 产物，但 P[三键]CrF3 除外，它是较高能量的物质，未观察到。 E[三键]MX3磷族金属三卤化物分子是通过密度泛函理论和多构型二阶微扰理论（CASSCF/CASPT2）计算的氩和氖矩阵红外光谱和频率来识别的。这些简单的末端氮化物涉及强三键，根据 CASSCF/CASPT2 计算，M = W、Mo 和 Cr 的自然键顺序范围分别为 2.80 至 2.77 至 2.59，并且 M[三键]N 拉伸频率也遵循此顺序。末端磷化物较弱，键级分别为 2.74、2.67 和 2.18，因为更分散的 3p 轨道对于与更紧凑的金属价 d 轨道的键合效果较差。
Organometallic complexes containing terminal metal nitrides and phosphides are important synthetic reagents. Laser-ablated group 6 metal atoms react with NF 3, PF 3, and PCl 3 to form the simple lowest energy N[triple bond]MF 3, and P[triple bond]MX 3 products following insertion and halogen transfer, with the exception of P[triple bond]CrF3, which is a higher energy species and is not observed. The E[triple bond]MX3 pnictide metal trihalide molecules are identified from both argon and neon matrix infrared spectra and frequencies calculated by density functional theory and multiconfigurational second-order perturbation theory (CASSCF/CASPT2). These simple terminal nitrides involve strong triple bonds, which range from 2.80 to 2.77 to 2.59 natural bond order for M = W, Mo, and Cr, respectively, as computed by CASSCF/CASPT2, and the M[triple bond]N stretching frequencies also follow this order. The terminal phosphides are weaker with bond orders 2.74, 2.67, and 2.18, respectively, as the more diffuse 3p orbitals are less effective for bonding to the more compact metal valence d orbitals.