Watt Fabian A, Dickmann Nicole, Schoch Roland, Hohloch Stephan
Paderborn University, Faculty of Science, Department of Chemistry, Warburger Straße 100, 33098 Paderborn, Germany.
University of Innsbruck, Faculty of Chemistry and Pharmacy, Institute of General, Inorganic and Theoretical Chemistry, Innrain 80-82, 6020 Innsbruck, Austria.
Inorg Chem. 2020 Sep 21;59(18):13621-13631. doi: 10.1021/acs.inorgchem.0c01971. Epub 2020 Sep 4.
A new route to heterobimetallic lanthanide-coinage-metal complexes is disclosed. The selective insertion of organic substrates such as phenyl iso(thio)cyanate into the La-P bond of the primary phosphido complex () (with PN = (-(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide) yields the phospha(thio)ureate complexes () and () with retention of the P protons. Subsequent deprotonation of the phosphaureate complex with potassium hexamethyldisilazide (KHMDS, K[N(SiMe)]) leads to the polymeric complex (). Complex was found to be an excellent precursor for salt metathesis reactions with copper(I) and gold(I) chlorides supported by an N-heterocyclic carbene (NHC, and ) or a cyclic alkyl amino carbene (CAAC, and ). This resulted in the unprecedented formation of heterobimetallic lanthanum-coinage-metal complexes, containing the first example of a μ,κ(,):κ()-phosphaureate bridging ligand. For an alternative route to complex a direct protonolysis protocol between a new basic gold(I) precursor, namely , and was also investigated. The complexes have been characterized by multinuclear NMR spectroscopy, IR spectroscopy, and X-ray crystallography (except for ).
本文公开了一种合成异双金属镧系元素-铜族金属配合物的新方法。将有机底物如异（硫）氰酸苯酯选择性插入到一级膦基配合物（）（其中PN =（-（2-（二异丙基膦基）-4-甲基苯基）-2,4,6-三甲基苯胺）的La-P键中，得到磷（硫）脲酸酯配合物（）和（），同时保留P质子。随后用六甲基二硅氮基钾（KHMDS，K[N(SiMe)₃]）对磷脲酸酯配合物（）进行去质子化反应，得到聚合物配合物（）。研究发现，配合物（）是与由N-杂环卡宾（NHC，和）或环烷基氨基卡宾（CAAC，和）支持 的氯化亚铜（I）和氯化亚金（I）进行盐复分解反应的优良前体。这导致了前所未有的异双金属镧系元素-铜族金属配合物的形成，其中包含首例μ,κ(³P,²N):κ²P-磷脲酸酯桥联配体。对于配合物（）的另一种合成路线，还研究了一种新的碱性金（I）前体即 与 之间的直接质子解反应方案。这些配合物已通过多核核磁共振光谱、红外光谱和X射线晶体学进行了表征（配合物（）除外）。
