Departamento de Química Orgánica, Univ. de Sevilla, Apdo. de Correos 1203, 41071, Seville, Spain.
Dalton Trans. 2009 Sep 21(35):7113-20. doi: 10.1039/b907043e. Epub 2009 Jul 21.
The reaction of [1,2,4]triazolo[4,3-a]pyridinium tetrafluoroborates with RhCl(COD) and PdCl(allyl) takes place under mild basic conditions (Et(3)N, THF, room temperature) to afford the corresponding [RhCl(COD)(Tripy)] and [PdCl(allyl)(Tripy)] complexes, respectively (Tripy = [1,2,4]triazolo[4,3-a]pyridin-3-ylidene), and their structures were analysed by X-ray diffractometry and spectroscopic techniques. The sigma-donor ability of the new ligands was estimated by comparative analysis of infrared nu(CO) stretching frequencies of [RhCl(CO)(2)(Tripy)] complexes, and proved to be strongly dependent on the substitution pattern. Additionally, a first insight into the catalytic properties of the latter in the Suzuki-Miyaura cross coupling demonstrates a good catalytic activity that enables the coupling of aryl chlorides at room temperature.
[1,2,4]三唑并[4,3-a]吡啶翁四氟硼酸盐与[RhCl(COD)]2 和[PdCl(allyl)]2 的反应在温和的碱性条件下(Et3N、THF、室温)进行,分别得到相应的[RhCl(COD)(Tripy)]和[PdCl(allyl)(Tripy)]配合物(Tripy=[1,2,4]三唑并[4,3-a]吡啶-3-亚基),并通过 X 射线衍射和光谱技术对其结构进行了分析。通过比较[RhCl(CO)(2)(Tripy)]配合物中红外 nu(CO)伸缩频率,评估了新配体的sigma-给体能力,结果表明其强烈依赖于取代模式。此外,初步研究了后者在铃木-宫浦交叉偶联反应中的催化性能,证明其具有良好的催化活性,能够在室温下实现芳基氯化物的偶联。