Osseili Hassan, Mukherjee Debabrata, Spaniol Thomas P, Okuda Jun
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany.
Chemistry. 2017 Oct 12;23(57):14292-14298. doi: 10.1002/chem.201702818. Epub 2017 Sep 18.
Alkali metal hydridotriphenylborates [(L )M][HBPh ] (L =Me TREN; M=Li, Na, K) chemoselectively catalyze the hydroboration of carbonyls and CO , with lithium being the most active system. A new series of complexes [(L )M][HBPh ] [M=Li (1), Na (2), K (3)] featuring the cyclen-derived macrocyclic polyamine Me TACD (L ) were synthesized in a "one-pot" fashion and fully characterized including X-ray crystallography. In the crystal, 1-3 exhibit wide variation in metal coordination of the [HBPh ] anion from lithium to potassium. The structures differ from those in [(L )M][HBPh ]. Effects of coordination of L , L , and other N- and O-donor multidentate ligands on [Li(HBPh )] were used to rationalize the catalytic activity in carbonyl hydroboration.
碱金属氢三苯基硼酸盐[（L ）M][HBPh ]（L =Me TREN；M=Li、Na、K）可化学选择性地催化羰基化合物和CO的硼氢化反应，其中锂的催化体系活性最高。通过“一锅法”合成了一系列以环醚衍生的大环多胺Me TACD（L ）为特征的新型配合物[（L ）M][HBPh ] [M=Li（1）、Na（2）、K（3）]，并通过X射线晶体学等手段进行了全面表征。在晶体中，1-3中[HBPh ]阴离子的金属配位情况从锂到钾呈现出很大差异。其结构与[（L ）M][HBPh ]中的结构不同。利用L 、L 以及其他N和O供体多齿配体与[Li(HBPh )]的配位作用来解释羰基硼氢化反应中的催化活性。
