Unexpected Photodegradation of a Phosphaketenyl-Substituted Germyliumylidene Borate Complex.
Unexpected Photodegradation of a Phosphaketenyl-Substituted Germyliumylidene Borate Complex.
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DOI：
10.1002/anie.201701337
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发表时间：
2017-04
影响因子：
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通讯作者：
Y. Xiong;Shenglai Yao;Tibor Szilvási;Ernesto Ballestero‐Martínez;H. Grützmacher;M. Driess
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文献类型：
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作者：
Y. Xiong;Shenglai Yao;Tibor Szilvási;Ernesto Ballestero‐Martínez;H. Grützmacher;M. Driess
通过[L2 (Cl)Ge:] 1 与钠的盐复分解反应合成了第一个两性离子硼酸双(NHC)稳定的磷酸烯基甲亚基[(L2 (O=C=P)Ge:] 2 (L2 =(p-tolyl)2 B[1-(1-金刚烷基)-3-基-2-亚基]2 ) 磷酸乙炔酯[(二恶烷)n NaOCP]。出乎意料的是，在还原消除整个PCO基团后，将其暴露于紫外光下，前所未有的[L2 Ge-GeL2 ]配合物3以54%的产率产生带有Ge22+离子的Ge22+离子，其中Ge处于氧化态+1。此外，1,3-二甲鎓-2,4-二磷环丁二烯 [L2 也可以中等产率获得Ge(μ-P)2 GeL2 ] 4 和双(甲亚基)取代的二磷吩[(L2 Ge-P=P-GeL2 )] 5 。 3-5的形成及其电子结构已通过DFT计算得到阐明。
The first zwitterionic borata-bis(NHC)-stabilized phosphaketenyl germyliumylidene [(L2 (O=C=P)Ge:] 2 (L2 =(p-tolyl)2 B[1-(1-adamantyl)-3-yl-2-ylidene]2 ) has been synthesized by salt-metathesis reaction of [L2 (Cl)Ge:] 1 with sodium phosphaethynolate [(dioxane)n NaOCP]. Unexpectedly, its exposure to UV light affords, after reductive elimination of the entire PCO group, the unprecedented [L2 Ge-GeL2 ] complex 3 in 54 % yields bearing the Ge22+ ion with Ge in the oxidation state +1. In addition, the 1,3-digermylium-2,4-diphosphacyclobutadiene [L2 Ge(μ-P)2 GeL2 ] 4 and bis(germyliumylidenyl)-substituted diphosphene [(L2 Ge-P=P-GeL2 )] 5 could also be obtained in moderate yields. The formation of 3-5 and their electronic structures have been elucidated with DFT calculations.