Divergent kinetic and thermodynamic acidity in organotransition-metal hydride complexes: synthesis, structure, and reactivity of the rhenium anion of Li+ [(.eta.-C5H5)Re(NO)(PPh3)]-
作者:Guy L. Crocco、John A. Gladysz
DOI:10.1021/ja00226a027
日期:1988.8
complex (/eta//sup 5/-C/sub 5/H/sub 5/)Re(NO)(PPh/sub 3/)(H) (1) and n-BuLi/TMEDA (THF, /minus/78/degree/C) gives (/eta//sup 5/-C/sub 5/H/sub 4/Li)Re(NO)(PPh/sub 3/)(H)(Li/sup +/-8), as shown by /sup 31/P NMR monitoring, deuterium labeling, and methylation (CH/sub 3/OSO/sub 2/CF/sub 3/, /minus/78/degree/C) to (/eta//sup 5/-C/sub 5/H/sub 4/CH/sub 3/)Re(NO)(PPh/sub 3/)(H) (9, 52%). Complex Li/sup +/-8 rearranges
氢化物络合物 (/eta//sup 5/-C/sub 5/H/sub 5/)Re(NO)(PPh/sub 3/)(H) (1) 和 n-BuLi/TMEDA (THF, /minus/78/degree/C) 给出 (/eta//sup 5/-C/sub 5/H/sub 4/Li)Re(NO)(PPh/sub 3/)(H)(Li/sup + /-8),如 /sup 31/P NMR 监测、氘标记和甲基化 (CH/sub 3/OSO/sub 2/CF/sub 3/, /minus/78/degree/C) 到 (/ eta//sup 5/-C/sub 5/H/sub 4/CH/sub 3/)Re(NO)(PPh/sub 3/)(H) (9, 52%)。络合物 Li/sup +/-8 重排为 Li/sup 的铼阴离子 +/((/eta//sup 5/-C/sub 5/H/sub 5/)Re(NO)(PPh/sub