Pérez Damaris E, Smeltz Jessica L, Sommer Roger D, Boyle Paul D, Ison Elon A
Department of Chemistry, North Carolina State University, 2620 Yarbrough Drive, Raleigh, North Carolina 27695-8204, USA.
Dalton Trans. 2017 Apr 5;46(14):4609-4616. doi: 10.1039/c7dt00271h.
A series of novel cationic Re(iii) complexes [(DAAm)Re(CO)(NCCH)][X] [DAAm = N,N-bis(2-arylaminoethyl)methylamine; aryl = CF (a), Mes (b)] [X = OTf (2), BAr [BAr = tetrakis[3,5-(trifluoromethyl)phenyl]borate] (3), BF (4), PF (5)], and their analogue [(DAmA)Re(CO)(Cl)] [DAmA = N,N-bis(2-arylamineethyl)methylamino; aryl = CF] (6) were synthesized. The catalytic efficiency for the hydrosilylation reaction of aldehydes using 4a (0.03 mol%) has been demonstrated to be significantly more active than rhenium catalysts previously reported in the literature. The data suggest that electron-withdrawing substituents at the diamido amine ligand increase the catalytic efficiency of the complexes. Excellent yields were achieved at ambient temperature under neat conditions using dimethylphenylsilane. The reaction affords TONs of up to 9200 and a TOF of up to 126 h. Kinetic and mechanistic studies were performed, and the data suggest that the reaction is via a non-hydride ionic hydrosilylation mechanism.
合成了一系列新型阳离子铼（III）配合物[(DAAm)Re(CO)(NCCH)][X] [DAAm = N,N-双(2-芳基氨基乙基)甲胺；芳基 = CF（a），Mes（b）] [X = OTf（2），BAr [BAr = 四[3,5-(三氟甲基)苯基]硼酸酯]（3），BF（4），PF（5）]，以及它们的类似物[(DAmA)Re(CO)(Cl)] [DAmA = N,N-双(2-芳基胺乙基)甲氨基；芳基 = CF]（6）。已证明使用4a（0.03 mol%）对醛的硅氢化反应的催化效率比文献中先前报道的铼催化剂显著更高。数据表明，二酰胺胺配体上的吸电子取代基提高了配合物的催化效率。在室温下使用二甲基苯基硅烷在纯态条件下获得了优异的产率。该反应的TON高达9200，TOF高达126 h。进行了动力学和机理研究，数据表明该反应是通过非氢化物离子硅氢化机理进行的。
