Dipartimento di Scienze e Tecnologie Chimiche, Università di Udine, Via Cotonificio 108, 33100 Udine, Italy.
Chemistry. 2011 Mar 14;17(12):3474-81. doi: 10.1002/chem.201003022. Epub 2011 Feb 21.
The ruthenium and osmium complexes [MCl(2)(diphosphane)(L)] (M=Ru, Os; L=bidentate amino ligand) and [MCl(CNN)(dppb)] (CNN=pincer ligand; dppb=1,4-bis-(diphenylphosphino)butane), containing the N−H moiety, have been found to catalyze the acceptorless dehydrogenation of alcohols in tBuOH and in the presence of KOtBu. The compounds trans-[MCl(2)(dppf)(en)] (M=Ru 7, Os 13; dppf=1,1'-bisdiphenylphosphino)ferrocene; en=ethylenediamine) display very high activity and different substrates, including cyclic and linear alcohols, are efficiently oxidized to ketones by using 0.8-0.04 mol % of catalyst. The effect of the base and the comparison of the catalytic activity of the Ru versus Os complexes are reported. The ruthenium complex 7 generally leads to a faster conversion into ketones with respect to the osmium complex 13, which displays better activity in the dehydrogenation of 5-en-3β-hydroxy steroids. The synthesis of new Ru and Os complexes [MCl(2)(PP)(L)] (PP=dppb, dppf; L=(±)-trans-1,2-diaminocyclohexane,2-(aminomethyl)pyridine, and 2-aminoethanol) of trans and cis configuration is also reported.
钌和锇的配合物 [MCl(2)(二膦烷)(L)]（M=Ru，Os；L=双齿氨基配体）和 [MCl(CNN)(dppb)]（CNN=钳形配体；dppb=1,4-双-(二苯基膦基)丁烷），含有 N−H 部分，已被发现可在 tBuOH 中和 KOtBu 的存在下催化醇的无受体脱氢。化合物 trans-[MCl(2)(dppf)(en)]（M=Ru 7，Os 13；dppf=1,1'-双二苯基膦基）二茂铁；en=乙二胺）显示出非常高的活性，不同的底物，包括环状和直链醇，可通过使用 0.8-0.04 mol%的催化剂有效地氧化为酮。报告了碱的影响以及 Ru 与 Os 配合物的催化活性比较。与 Os 配合物 13 相比，钌配合物 7 通常导致更快地转化为酮，而 13 配合物在 5-烯-3β-羟基甾体的脱氢反应中表现出更好的活性。还报道了新型 Ru 和 Os 配合物 [MCl(2)(PP)(L)]（PP=dppb，dppf；L=(±)-反式-1,2-二氨基环己烷、2-(氨甲基)吡啶和 2-氨基乙醇）的顺式和反式构型的合成。
