Harris Lisa M, Tam Eric C Y, Cummins Struan J W, Coles Martyn P, Fulton J Robin
Department of Chemistry, University of Sussex , Falmer, Brighton BN1 9QJ, United Kingdom.
School of Chemical and Physical Sciences, Victoria University of Wellington , P.O. Box 600, Wellington 6012, New Zealand.
Inorg Chem. 2017 Mar 6;56(5):3087-3094. doi: 10.1021/acs.inorgchem.6b03109. Epub 2017 Feb 17.
The reactivity of germanium phosphanido complexes with elemental chalcogens is reported. Addition of sulfur to [(BDI)GePCy] (BDI = CH{(CH)CN-2,6-iPrCH}) results in oxidation at germanium to form germanium(IV) sulfide [(BDI)Ge(S)PCy] and oxidation at both germanium and phosphorus to form germanium(IV) sulfide dicylohexylphosphinodithioate complex [(BDI)Ge(S)SP(S)Cy], whereas addition of tellurium to [(BDI)GePCy] only gives the chalcogen inserted product, [(BDI)GeTePCy]. This reactivity is different from that observed between [(BDI)GePCy] and selenium. Addition of selenium to the diphenylphosphanido germanium complex, [(BDI)GePPh], results in insertion of selenium into the Ge-P bond to form [(BDI)GeSePCy] as well as the oxidation at phosphorus to give [(BDI)GeSeP(Se)Ph]. In contrast, addition of selenium to the bis(trimethylsilyl)phosphanido germanium complex, [(BDI)GeP(SiMe)], yields the germanium(IV) selenide [(BDI)Ge(Se)P(SiMe)].
报道了锗膦基配合物与元素硫族元素的反应活性。将硫加入到[(BDI)GePCy]（BDI = CH{(CH)CN-2,6-iPrCH}）中，会导致锗发生氧化形成硫化锗(IV) [(BDI)Ge(S)PCy]，以及锗和磷都发生氧化形成二硫化锗二环己基膦酸酯配合物[(BDI)Ge(S)SP(S)Cy]，而将碲加入到[(BDI)GePCy]中只会得到硫族元素插入产物[(BDI)GeTePCy]。这种反应活性与[(BDI)GePCy]和硒之间观察到的不同。将硒加入到二苯基膦基锗配合物[(BDI)GePPh]中，会导致硒插入到Ge-P键中形成[(BDI)GeSePCy]，以及磷发生氧化生成[(BDI)GeSeP(Se)Ph]。相比之下，将硒加入到双(三甲基硅基)膦基锗配合物[(BDI)GeP(SiMe)]中，会生成硒化锗(IV) [(BDI)Ge(Se)P(SiMe)]。
