作者:Sebastian Schrader、Priyabrata Ghana、Alexander Hoffmann、Thomas P. Spaniol、Jun Okuda
DOI:10.1021/acs.organomet.2c00566
日期:——
calculations. Hydrogenation in THF at 25 °C reformed the hydride complex over a period of 48 h. The hydride complex reacted with olefins RHC═CH2 (R = H, Et, nHex, cHex, Ph) to give the corresponding anti-Markovnikov insertion products [Hf(CH2CH2R)(thf)n(Xy-N3N)]. Catalytic hydrogenation of olefins was achieved with 5 mol % of the hydride complex at 70 °C in THF or benzene.
由芳基取代的三氨基胺配体 [HfH(thf)(Xy-N 3 N)] (Xy-N 3 N = (3,5-Me 2 C 6 H 3 )NCH 2 CH 2 } 3 N 3– ) 通过烃基络合物 [Hf(R)(thf)(Xy-N 3 N)] (R = Me, CH 2 SiMe 3 , η 3 -C 3 H 5 , CH 2 Ph) 在四氢呋喃 (THF) 中,或者更方便地,通过氯前体 [HfCl(thf)(Xy-N 3 N)] 与 NaBEt 3的盐置换H 在甲基环己烷中。通过单晶 X 射线衍射 ( d (Hf–H): 1.83(3) Å) 和1 H NMR 光谱表征具有扭曲封端三角双锥几何结构的末端氢化物的结构。在 δ 18.28 ppm 处检测到氢化物配体异常低的场位移1 H 化学位移。氢化物配合物在 25 °C 下在苯或甲苯中的脱氢热解导致配体中三个 XyNCH 2 CH 2基团之一的