摘要
利用三乙胺对配合物[TpRu(PPh3)2(H2O)]BF4脱质子化合成了氢氧根钌配合物TpRu(PPh3)2(OH),并研究了TpRu(PPh3)2(OH)催化水化乙腈的反应。机理研究表明,催化循环的关键中间体为氧配位的酰亚胺配合物TpRu(PPh3)(CH3CN)(OCMe=NH),经过生成TpRu(PPh3)(κ2-N,O-NH=CMeN=CMeO)、水亲核进攻开环生成TpRu(PPh3)(NH=C(OH)Me)(OCMe=NH)、乙腈取代其NH=C(OH)Me配体产生乙酰胺、同时生成TpRu(PPh3)(CHCN)(OCMe=NH)完成催化循环。
Ruthenium hydroxo complex TpRu(PPh3)2 (OH) has been synthesized by deprotonation of [-Tp- Ru(PPh3)2 (H20)-]BF4 in the presence of triethyl amine. The catalytic hydration of acetonitrile by TpRu (PPh3)2 (OH) is studied. The catalytic mechanism is proposed that O-bonded imido complex TpRu(PPb3) (CH3CN)(OCMe=NH) is the key intermediate, which then undergoes nucleophilic attack at the carbon atom of nitrile ligand to form TpRu(PPh3)(k^2 -N ,O-NH=CMeN=CMeO). Ring-opening necleophilic attack of TpRu(PPh3 ) (k^2 -N ,O-NH = CMeN= CMeO) by water pruduces TpRu(PPh3 ) (NH = C(OH) Me) (OCMe= NH). The displacement of NH = C(OH)Me ligand in the latter complex by acetonitrile forms acetamide, and regenerates TpRu(PPh3)(CH3CN)(OCMe=NH) to fulfill the catalytic cycle.
出处
《化学与生物工程》
CAS
2009年第8期25-28,共4页
Chemistry & Bioengineering
基金
湖北省自然科学基金资助项目(2006ABA282)
湖北省教育厅基金资助项目(D200615005)
关键词
氢氧根钌配合物
乙腈
催化水化
机理
ruthenium hydroxo complex
acetonitrile
catalytic hydration
mechanism