Pretorius René, Fructos Manuel R, Müller-Bunz Helge, Gossage Robert A, Pérez Pedro J, Albrecht Martin
Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
Dalton Trans. 2016 Oct 7;45(37):14591-602. doi: 10.1039/c6dt02181f. Epub 2016 Jul 1.
A series of novel 1,2,3-triazolylidene gold(i) chloride complexes have been synthesised and fully characterised. Silver-free methodologies for chloride ion abstraction of these complexes were evaluated for their potential as Au-based catalyst precursors. Using simple potassium salts or MeOTf as chloride scavengers produced metal complexes that catalyse both the regioselective synthesis of oxazolines and the C-H activation of benzene or styrene for carbene transfer from ethyl diazoacetate. These results indicate that Ag-free activation of 1,2,3-triazolylidene gold(i) chloride complexes is feasible for the generation of catalytically active Au triazolylidene species. However, silver-mediated activation imparts substantially higher catalytic activity in oxazoline synthesis.
一系列新型的1,2,3 - 三唑亚基氯化金（I）配合物已被合成并完全表征。评估了用于这些配合物氯离子提取的无银方法作为金基催化剂前体的潜力。使用简单的钾盐或三氟甲磺酸甲酯作为氯清除剂可生成金属配合物，这些配合物既能催化恶唑啉的区域选择性合成，又能催化苯或苯乙烯的C - H活化以实现重氮乙酸乙酯的卡宾转移。这些结果表明，1,2,3 - 三唑亚基氯化金（I）配合物的无银活化对于生成具有催化活性的金三唑亚基物种是可行的。然而，银介导的活化在恶唑啉合成中赋予了更高的催化活性。
