Simultaneous Harvesting of Multiple Hot Holes via Visible-Light Excitation of Plasmonic Gold Nanospheres for Selective Oxidative Bond Scission of Olefins to Carbonyls

Using visible photoexcitation of gold nanospheres we successfully demonstrate the simultaneous harvesting of plasmon-induced multiple hot holes in the complete oxidative scission of the C=C bond in styrene at room temperature to selectively form benzaldehyde and formaldehyde, which is a reaction that requires activation of multiple substrates. Our results reveal that, while extraction of hot holes becomes efficient for interband excitation, harvesting of multiple hot holes from the excited Au nanospheres becomes prevalent only beyond a threshold light intensity. We show that the alkene oxidation proceeded via a sequence of two consecutive elementary steps; namely, a binding step and a cyclic oxometallate transition state as the rate-determining step. This demonstration of plasmon-excitation-mediated harvesting of multiple hot holes without the use of an extra hole transport media opens exciting possibilities, notably for difficult catalytic transformations involving multielectron oxidation processes.     

新型手性双二茂铁希呋碱亚胺配体的合成及其在不对称环丙烷化反应中的应用

以手性二茂铁乙胺为手性前体分别与吡啶二醛和吡啶二酮进行希呋碱缩合反应，合成了两种二茂铁手性亚胺膦配体，并经元素分析，^1HNMR，^31PNMR等手段进行了表征，用这类化合物作为手性配体，研究了其金属Ru(Ⅱ)配合物对苯乙烯与重氮乙酸乙酯的不对称环丙烷反应的催化作用，结果表明该类化合物的Ru(Ⅱ)配合物具有很高的催化活性。