Remarkably Favorable Hydration of Carbonyl Substituents in Dicationic Bis(arene) Ruthenium Complexes

The addition of water and methanol to the carbonyl substituents in the dicationic bis(arene)ruthenium complexes [(p-cymene)Ru(C6H5CHO)][OTf]2 (1) and [(p-cymene)Ru(C6H5C(O)CH3)][OTf]2 (2) is remarkably favorablethe equilibrium constants for these reactions are 1 million times greater than those for uncomplexed benzaldehyde and acetophenone. The addition of methanol to the carbonyl group in the o-anisaldehyde complex, [(p-cymene)Ru(C6H4{OCH3}CHO)][OTf]2 (6), occurs with a high degree of kinetic selectivity (94% de).

在双阳离子双(芳烃)钌配合物[(对伞花烃)Ru(C₆H₅CHO)][三氟甲磺酸盐(OTf)]₂（编号1）与[(对伞花烃)Ru(C₆H₅C(O)CH₃)][三氟甲磺酸盐(OTf)]₂（编号2）的羰基官能团位点上，水与甲醇的加成反应热力学可行性极强——此类反应的平衡常数较未配位的苯甲醛和苯乙酮的对应反应高出百万倍。在邻茴香醛配合物[(对伞花烃)Ru(C₆H₄(OCH₃)CHO)][三氟甲磺酸盐(OTf)]₂（编号6）中，甲醇对羰基的加成反应展现出极高的动力学选择性，非对映体过量率(de)达94%。