Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organometallici, Via Madonna del Piano 10, 50019 Sesto Fiorentino (Firenze), Italy.
Dalton Trans. 2013 Mar 14;42(10):3533-41. doi: 10.1039/c2dt32273k. Epub 2013 Jan 2.
Catalytic dehydrogenation of ammonia-borane (NH(3)·BH(3), AB) and dimethylamine borane (NHMe(2)·BH(3), DMAB) by the Pd(II) complex [((tBu)PCP)Pd(H(2)O)]PF(6) [(tBu)PCP = 2,6-C(6)H(3)(CH(2)P(t)Bu(2))(2)] leads to oligomerization and formation of spent fuels of general formula cyclo-BH(2)-NR(2) (n = 2,3; R = H, Me) as reaction byproducts, while one equivalent of H(2) is released per amine-borane equivalent. The processes were followed through multinuclear ((31)P, (1)H, (11)B) variable temperature NMR spectroscopy; kinetic measurements on the hydrogen production rate and the relative rate constants were also carried out. One non-hydridic intermediate could be detected at low temperature, whose chemical nature was explored through a DFT modeling of the reaction mechanism, at the M06//6-31+G(d,p) computational level. The computational output was of help to propose a reliable mechanistic picture of the process.
钯（II）配合物[((tBu)PCP)Pd(H(2)O)]PF(6) [(tBu)PCP = 2,6-C(6)H(3)(CH(2)P(t)Bu(2))(2)]催化氨硼烷（NH(3)·BH(3)，AB）和二甲胺硼烷（NHMe(2)·BH(3)，DMAB）的脱氢反应导致齐聚物的形成和一般式环-BH(2)-NR(2) (n = 2,3; R = H, Me)的废燃料的形成，作为反应的副产物，同时每胺硼烷当量释放一个当量的 H(2)。通过多核（(31)P、(1)H、(11)B）变温 NMR 光谱跟踪这些过程；还进行了产氢速率和相对速率常数的动力学测量。在低温下可以检测到一种非氢化物中间体，通过在 M06//6-31+G(d,p)计算水平上对反应机理进行的 DFT 建模，研究了其化学性质。计算结果有助于提出该过程可靠的机理图。
