Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany) http://www-anorganik.chemie.uni-wuerzburg.de/Braunschweig/
Angew Chem Int Ed Engl. 2014 Feb 17;53(8):2240-4. doi: 10.1002/anie.201310557. Epub 2014 Jan 22.
The reaction of [Pt(PCy3)2] with Br2B-CH(SiMe3)2 resulted in generation of the first alkylideneboryl complex, trans-[Br(Cy3P)2Pt{B=CH(SiMe3)}], with concomitant elimination of Me3 SiBr. The trans bromide ligand of the alkylideneboryl complex was readily substituted by a methyl group upon treatment with methyllithium, leading to another alkylideneboryl complex, trans-[Me(Cy3P)2Pt{B=CH(SiMe3)}]. Various spectrochemical techniques, single-crystal X-ray crystallography, and quantum chemical calculations confirmed the formulation of a double bond between the boron and the carbon atom. The theoretical studies also provided evidence for the stronger trans influence of the alkylideneboryl ligand over iminoboryl and oxoboryl ligands.
[Pt(PCy3)2]与 Br2B-CH(SiMe3)2 的反应生成了第一个亚烷基硼基配合物,反式-[Br(Cy3P)2Pt{B=CH(SiMe3)}],同时消除了 Me3SiBr。亚烷基硼基配合物的反式溴配体很容易被甲基锂取代,生成另一个亚烷基硼基配合物,反式-[Me(Cy3P)2Pt{B=CH(SiMe3)}]。各种光谱化学技术、单晶 X 射线晶体学和量子化学计算证实了硼原子和碳原子之间双键的形成。理论研究还为亚烷基硼基配体相对于亚胺硼基和氧硼基配体的更强的反式影响提供了证据。