双齿N基配体锇配合物的合成及其在催化氨硼烷释氢中的应用

Synthesis of Osmium Complexes with Bidentate Nitrogen-Based Ligands and Their Application in Catalytic Dehydrogenation of Ammonia Borane

OsCl_2(PPh_3)_3 (1)与双齿N基配体乙二胺、取代/非取代邻苯二胺和取代/非取代1,10-菲啰啉(Phen*)在室温下反应,可分别生成锇配合物OsCl_2(PPh_3)_2(diamine)(2～6)和OsCl_2(PPh_3)_2(Phen*)(7～11).研究表明, 2～11作为催化剂在60℃时,以四氢呋喃(THF)/乙二醇二甲醚(DME)(体积比1∶1.6)为溶剂,催化剂负载量为5 mol%的条件下,具有高效的催化氨硼烷脱氢反应活性.其中,3-甲基-邻苯二胺取代的锇配合物4催化氨硼烷脱氢活性最高,它也是目前报道的最高效的氨硼烷脱氢锇催化剂.

Reactions of OsCl2(PPh3)3(1) with bidentate nitrogen-based ligands at room temperature led to the formation of complexes OsCl2(PPh3)2(diamine)(2~6) and OsCl2(PPh3)2(Phen*)(7~11). Complexes 2~11 showed high activity in the catalytic dehydrogenation of ammonia borane at 60 ℃, in THF/DME(V∶V=1∶1.6) solution with the catalyst loading of 5mol%. Among all the catalysts, compound 4 demonstrated the highest catalytic activity, which represents the most efficient osmium catalyst in catalytic dehydrogenation of ammonia borane until now.