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Highly efficient formic acid dehydrogenation using bio-inspired Ir complexes: A deuterium kinetic isotope effect study and mechanistic insight

2014-5-21 23:01| 发布者: Mcdull| 查看: 2018| 评论: 0|原作者: whui10001|来自: 捷报频传

摘要: 去年元旦前投的,2个月左右返回修改意见,一个大修,两个小修。这时我已经离开AIST,回国工作了。修改完,再投之后,竟然又等了2个月。而让大修的那个审稿人也基本没什么问题,两个月不知在搞什么东东。好在编辑根据 ...
作者:
Wang, W.-H.; Xu, S.; Manaka Y.; Suna, Y.; Kambayashi, H.; Muckerman, J. T.; Fujita, E.; Himeda, Y.*

期刊:
Chemsuschem
2014, early view.

Keywords:
dehydrogenation;
formic acid;
hydrogen;
iridium;
isotope effects

Abstract
Highly efficient hydrogen generation from dehydrogenation of formic acid is achieved by using bioinspired iridium complexes that have hydroxyl groups at the ortho positions of the bipyridine or bipyrimidine ligand (i.e., OH in the second coordination sphere of the metal center). In particular, [Ir(Cp*)(TH4BPM)(H2O)]SO4 (TH4BPM: 2,2′,6,6′-tetrahydroxyl-4,4′-bipyrimidine; Cp*: pentamethylcyclopentadienyl) has a high turnover frequency of 39 500 h−1 at 80 °C in a 1 M aqueous solution of HCO2H/HCO2Na and produces hydrogen and carbon dioxide without carbon monoxide contamination. The deuterium kinetic isotope effect study clearly indicates a different rate-determining step for complexes with hydroxyl groups at different positions of the ligands. The rate-limiting step is β-hydrogen elimination from the iridium–formate intermediate for complexes with hydroxyl groups at ortho positions, owing to a proton relay (i.e., pendent-base effect), which lowers the energy barrier of hydrogen generation. In contrast, the reaction of iridium hydride with a proton to liberate hydrogen is demonstrated to be the rate-determining step for complexes that do not have hydroxyl groups at the ortho positions.

http://onlinelibrary.wiley.com/d ... 9D5EC82E4784.f01t02

去年元旦前投的,2个月左右返回修改意见,一个大修,两个小修。这时我已经离开AIST,回国工作了。修改完,再投之后,竟然又等了2个月。而让大修的那个审稿人也基本没什么问题,两个月不知在搞什么东东。好在编辑根据意见立马给接收了。感觉这次文字编辑排版的速度加快了,很快文章就online了。但是国内高校都要求要第一单位,文章发表了虽然高兴。:) 但是学校不给算业绩,有点失落。:(

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