PPh3-substituted [2,5-Ph2-3,4-Tol2(η5-C4COH)]Ru(CO)(PPh3)H exhibits slower stoichiometric reduction, faster catalytic hydrogenation, and higher chemoselectivity for hydrogenation of aldehydes over ketones than the dicarbonyl Shvo catalyst
PPh3-substituted [2,5-Ph2-3,4-Tol2(η5-C4COH)]Ru(CO)(PPh3)H exhibits slower stoichiometric reduction, faster catalytic hydrogenation, and higher chemoselectivity for hydrogenation of aldehydes over ketones than the dicarbonyl Shvo catalyst
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DOI：
10.1021/om050939z
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发表时间：
2006-02-27
期刊：
影响因子：
2.8
通讯作者：
Guzei, IA
中科院分区：
文献类型：
--
作者：
Casey, CP;Strotman, NA;Guzei, IA
在吡啶陷阱存在下，PPh_3取代的羟基环戊二烯基钌氢化物[2，5-Ph-2-3，4-Tol(2)(eta(5)-C4COH]Ru(CO)(PPh3)H(1)以化学计量比还原醛和酮，生成醇和Ru-吡啶络合物5，其速率定律仅取决于[醛]和[1]。1的酸性质子和氢质子取代的动力学同位素效应与还原过程中氢向醛的协同转移是一致的。1在温和的温度和压力条件下催化加氢缩醛。虽然SHVO催化剂2在这些条件下表现出很小的活性，但它在高温和压力下超过了I。1对醛的催化加氢比酮表现出高的化学选择性，而2的选择性要低得多。
The PPh3-substituted hydroxycyclopentadienyl ruthenium hydride [2,5-Ph-2-3,4-Tol(2)(eta(5)-C4COH]Ru(CO)(PPh3)H (1) stoichiometrically reduces aldehydes and ketones in the presence of a pyridine trap to produce alcohols and the ruthenium pyridine complex 5, with a rate law that is dependent only on [aldehyde] and [1]. The observation of deuterium kinetic isotope effects on substitution of the acidic and hydridic protons of 1 are consistent with concerted transfer of hydrogen to aldehydes during reduction. 1 catalytically hydrogenates aldehydes under mild temperature and pressure conditions. While the Shvo catalyst 2 shows little activity under these conditions, it surpasses I at elevated temperatures and pressures. 1 shows high chemoselectivity for catalytic hydrogenation of aldehydes over ketones, while 2 is much less selective.