Department of Chemistry, University of Toronto. Toronto, Ontario M5S 3H6, Canada.
J Am Chem Soc. 2015 Apr 29;137(16):5582-9. doi: 10.1021/jacs.5b02203. Epub 2015 Apr 20.
A new family of ruthenium complexes bearing the carbodicarbene-type ligand "cyclic bent allene" (CBA) have been synthesized from the common precursor RuHCl(CO)(PPh3)3. Complexes were evaluated for catalytic activity in the room-temperature hydrogenation of unactivated olefins and were found to be significantly more active than known ruthenium hydrido-carbonyl phosphine or NHC complexes. In particular, RuH(OSO2CF3)(CO)(SIMes)(CBA) was found to be among the most active hydrogenation catalysts, achieving comparable activity to Crabtree's catalyst in the hydrogenation of unactivated trisubstituted olefins and superior activity in the hydrogenation of styrene derivatives in side-by-side catalytic runs. RuH(OSO2CF3)(CO)(SIMes)(CBA) was also found to be highly active in olefin selective hydrogenation in the presence of a variety of unsaturated functional groups, and can achieve exceptional diastereoselectivity in functional-group-directed hydrogenations at very low catalyst loadings.
一个新的钌配合物家族，承载了“环状弯曲丙二烯”（CBA）的碳二亚胺型配体，已从常见的前体 RuHCl(CO)(PPh3)3 合成。评估了配合物在室温下对未活化烯烃的催化加氢活性，发现它们比已知的钌氢羰基膦或 NHC 配合物具有显著更高的活性。特别是，RuH(OSO2CF3)(CO)(SIMes)(CBA)被发现是最活跃的加氢催化剂之一，在未活化三取代烯烃的加氢中与 Crabtree 的催化剂相当，在苯乙烯衍生物的加氢中具有优越的活性。在存在各种不饱和官能团的情况下，RuH(OSO2CF3)(CO)(SIMes)(CBA)在烯烃选择性加氢中也具有很高的活性，并且可以在非常低的催化剂负载下实现官能团定向加氢的优异非对映选择性。
