Center for Computational Quantum Chemistry, South China Normal University, Guangzhou 510631, PR China.
J Phys Chem A. 2010 Aug 26;114(33):8896-901. doi: 10.1021/jp103051s.
The stable tetrahedral derivative Ni(PF(3))(4) is reported to generate binuclear Ni(2)(PF(3))(n) ions in its mass spectrum emerging from ion-molecule reactions. Theoretical studies on such binuclear complexes indicate Ni(2)(PF(3))(7) to be energetically unfavorable with respect to decomposition into Ni(PF(3))(4) + Ni(PF(3))(3). However, viable rather unsymmetrical structures with two PF(3) bridges for Ni(2)(PF(3))(n) (n = 6, 5, 4) are reported here as well as a triply semibridged Ni(2)(PF(3))(5) structure. The nickel-nickel distances in these Ni(2)(PF(3))(n) derivatives suggest a formal double bond (2.51 A), a formal triple bond (2.26 A), and a formal double bond (2.34 A) for n = 6, 5, and 4, respectively. The mononuclear Ni(PF(3))(n) derivatives are predicted to have tetrahedral, trigonal planar, and bent (139 degrees ) structures for n = 4, 3, and 2, respectively.
据报道，稳定的四面体型衍生物 Ni(PF(3))(4)在其离子-分子反应产生的质谱中会生成双核 Ni(2)(PF(3))(n)离子。对这种双核配合物的理论研究表明，Ni(2)(PF(3))(7)相对于分解为 Ni(PF(3))(4) + Ni(PF(3))(3)来说是能量不利的。然而，本文还报道了 Ni(2)(PF(3))(n) (n = 6, 5, 4)具有两个 PF(3)桥的可行但不太对称的结构，以及一个三重半桥接的 Ni(2)(PF(3))(5)结构。这些 Ni(2)(PF(3))(n)衍生物中的镍-镍距离表明 n = 6、5 和 4 时分别具有形式双键(2.51 A)、形式三键(2.26 A)和形式双键(2.34 A)。预测单核 Ni(PF(3))(n)衍生物的结构分别为四面体、三角平面和弯曲(139 度)，对于 n = 4、3 和 2。
