Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organometallici (ICCOM-CNR), via Madonna del Piano 10, 50019, Sesto Fiorentino (Firenze), Italy.
Dalton Trans. 2011 May 7;40(17):4447-52. doi: 10.1039/c0dt01836h. Epub 2011 Apr 12.
Reaction of the pincer hydride complex ((tBu)PCP)Ni(H) [(tBu)PCP = 2,6-C(6)H(3)(CH(2)P(t)Bu(2))(2)] with BH(3)·thf in THF at 190 K generates the corresponding borohydride complex ((tBu)PCP)Ni(BH(4)). The kinetically stable (but thermodynamically unstable) species undergoes reversible borane loss. The related fluoride complex ((tBu)PCP)Ni(F) shows the same reactivity towards BF(3)·Et(2)O, producing ((tBu)PCP)Ni(BF(4)) as the main final product. The processes were followed through multinuclear NMR spectroscopy and DFT calculations, at the M06//6-31+G(d,p) level of theory.
膦夹氢配合物((tBu)PCP)Ni(H)[((tBu)PCP)=2,6-C(6)H(3)(CH(2)P(t)Bu(2))(2)]与 BH(3)·thf 在 190 K 下的 THF 中反应，生成相应的硼氢化物配合物((tBu)PCP)Ni(BH(4))。动力学稳定（但热力学不稳定）的物种经历可逆的硼烷损失。相关的氟化物配合物((tBu)PCP)Ni(F)对 BF(3)·Et(2)O 表现出相同的反应性，生成((tBu)PCP)Ni(BF(4))作为主要的最终产物。这些过程通过多核 NMR 光谱和 DFT 计算进行了跟踪，在 M06//6-31+G(d,p)理论水平上。
