Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
Department of Chemical & Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, WI, 53706, USA.
Angew Chem Int Ed Engl. 2017 Apr 3;56(15):4333-4336. doi: 10.1002/anie.201701337. Epub 2017 Mar 13.
The first zwitterionic borata-bis(NHC)-stabilized phosphaketenyl germyliumylidene [(L (O=C=P)Ge:] 2 (L =(p-tolyl) B[1-(1-adamantyl)-3-yl-2-ylidene] ) has been synthesized by salt-metathesis reaction of [L (Cl)Ge:] 1 with sodium phosphaethynolate [(dioxane) NaOCP]. Unexpectedly, its exposure to UV light affords, after reductive elimination of the entire PCO group, the unprecedented [L Ge-GeL ] complex 3 in 54 % yields bearing the Ge ion with Ge in the oxidation state +1. In addition, the 1,3-digermylium-2,4-diphosphacyclobutadiene [L Ge(μ-P) GeL ] 4 and bis(germyliumylidenyl)-substituted diphosphene [(L Ge-P=P-GeL )] 5 could also be obtained in moderate yields. The formation of 3-5 and their electronic structures have been elucidated with DFT calculations.
首例两性离子硼双(NHC)-稳定膦亚烯基锗叶立德[(L(O=C=P)Ge:]2(L=(对甲苯基)B[1-(1-金刚烷基)-2-亚基])由[L(Cl)Ge:]1与叠氮磷酸钠[(二氧六环)NaOCP]经盐交换反应合成。出人意料的是，它在紫外线照射下，经整个 PCO 基团还原消除后，以 54%的收率得到了前所未有的[LGe-GeL]配合物 3，该配合物中 Ge 离子的氧化态为+1。此外，还以中等产率得到了 1,3-二锗亚基-2,4-二膦环丁二烯[LGe(μ-P)GeL]4和双(亚烯基)取代的二磷杂环戊二烯[(LGe-P=P-GeL)]5。通过密度泛函理论(DFT)计算阐明了 3-5 的形成及其电子结构。
