From disilene (Si=Si) to phosphasilene (Si=P) and phosphacumulene (P=C=N).
From disilene (Si=Si) to phosphasilene (Si=P) and phosphacumulene (P=C=N).
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DOI：
10.1002/anie.201308525
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发表时间：
2014-02
影响因子：
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通讯作者：
Philipp Willmes;Michael J. Cowley;M. Hartmann;Michael Zimmer;V. Huch;D. Scheschkewitz
中科院分区：
文献类型：
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作者：
Philipp Willmes;Michael J. Cowley;M. Hartmann;Michael Zimmer;V. Huch;D. Scheschkewitz
生成较重的双键体系而不形成副产物对于它们在合成中的应用是相当重要的。在这方面，由于其固有的流动性，这种烯烃同系物中的外围官能团是有希望的。根据N-烷基取代基R的空间位阻需求，二硅烯Ar 2 Si =Si（Ar）Li（Ar = 2，4，6-iPr 3C 6 H2）与ClP（NR 2）2的反应要么提供膦基二硅烯Ar 2 Si=Si（Ar）P（NR 2）2（对于R = iPr），要么提供P-氨基官能化的磷硅烯Ar 2（R2 N）Si=Si（Ar）=P（NR 2）（对于R = Et、Me）通过一个氨基的1，3-迁移。在R = Me的情况下，在加入1当量叔丁基异腈时，发生第二次氨基移位，得到具有明显叶立德特征的1-氮杂-3-磷杂丙二烯Ar 2（R2 N）Si=Si（NR 2）（Ar）-P=C=NtBu。所有新化合物的充分特点是多核NMR光谱以及单晶X射线衍射和DFT计算在选定的情况下。
The generation of heavier double-bond systems without by- or side-product formation is of considerable importance for their application in synthesis. Peripheral functional groups in such alkene homologues are promising in this regard owing to their inherent mobility. Depending on the steric demand of the N-alkyl substituent R, the reaction of disilenide Ar2Si=Si(Ar)Li (Ar = 2,4,6-iPr3C6H2) with ClP(NR2)2 either affords the phosphinodisilene Ar2 Si=Si(Ar)P(NR2)2 (for R = iPr) or P-amino functionalized phosphasilenes Ar2(R2N)Si=Si(Ar)=P(NR2) (for R = Et, Me) by 1,3-migration of one of the amino groups. In case of R = Me, upon addition of one equivalent of tert-butylisonitrile a second amino group shift occurs to yield the 1-aza-3-phosphaallene Ar2(R2N)Si=Si(NR2)(Ar)-P=C=NtBu with pronounced ylidic character. All new compounds were fully characterized by multinuclear NMR spectroscopy as well as single-crystal X-ray diffraction and DFT calculations in selected cases.