Dichlorosilylene Transfer to a P-Fluorophosphaalkene: The Route to a C-Dichlorofluorosilyl-Functionalized Dialkyldiphosphene
Dichlorosilylene Transfer to a P-Fluorophosphaalkene: The Route to a C-Dichlorofluorosilyl-Functionalized Dialkyldiphosphene
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二氯亚甲硅烷基转移至对氟磷烯：生成 C-二氯氟甲硅烷基官能化二烷基二磷烯的路线
DOI：
10.1002/ejic.201601411
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
and Heinrich C. Marsmann
中科院分区：
文献类型：
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作者：
Cristina Mitrofan;Thorsten Gust;Andreas Zanin;Roxana M. Birzoi;Peter G. Jones;Wolf-W. du Mont;Satoko Hayashi;Waro Nakanishi;and Heinrich C. Marsmann
（三氯硅基）锗烷Me 3GeSiCl 3和不对称二硅烷Me 3SiSiCl 3与P-氟代磷烯（Me 3Si）2C=PF（1）的反应伴随着SiCl 2（2）的转移而进行，得到新的C-二氯氟硅基官能化的二烷基二膦（Cl 2FSi）（Me 3Si）2CP=PC（SiCl 2F）（SiMe 3）2（6），其通过X射线晶体学表征。通过31 P NMR光谱在反应混合物中检测到P-膦酰基磷烯（Me 3Si）2C=PP[C（SiCl 2F）（SiMe 3）2] SiCl 2F（8a），伴随着其异构体8b，推测为（Cl 2FSi）（Me 3Si）C=PP[C（SiCl 2F）（SiMe 3）2] SiMe 3。不对称二聚体8a和8b通过1，3-（P→C）甲硅烷基移位排列，提供反对称二磷杂苯6。化合物6与硒一起转化为硒二磷杂蒽（9）。对从1和2到亚稳态不对称二聚体8a和8b的中间体进行了量子化学计算。将SiCl 2加成到1的P=C键上，然后使硅磷杂环己烷4开环，得到亚膦基（Me 3Si）2（Cl 2FSi）CP（5），其进一步重排为异构的P-甲硅烷基磷烯（Me 3Si）2C= PSiCl 2F（7a）和（Cl 2FSi）（Me 3Si）C= PSiMe 3（7 b）。5与7a和7 b的快速膦酰基-磷烯P-P偶联反应，随后叶立德型二聚体11 a和11b的1，2-（P→P）硅基移位解释了观察到的物种8a和8b的形成。在之前的P-氯代磷烯（Me 3Si）2C=PCl（1′）与Si 2Cl 6、Me 3GeSiCl 3和Me 3SiSiCl 3反应的实验中，没有发现与8相关的物种，这使我们认为，在P-氯代磷烯的情况下，亲核试剂支持的SiCl 2插入P-Cl键或取代的Cl-/SiCl 3-交换是亚稳态P-（三氯甲硅烷基）磷烯（Me 3Si）2C= PSiCl 3的优选途径。
Reactions of the (trichlorosilyl)germane Me3GeSiCl3and of the unsymmetric disilane Me3SiSiCl3with theP‐fluorophosphaalkene (Me3Si)2C=PF (1) proceed with transfer of SiCl2(2) leading to the newC‐dichlorofluorosilyl‐functionalized dialkyldiphosphene (Cl2FSi)(Me3Si)2CP=PC(SiCl2F)(SiMe3)2(6), which was characterized by X‐ray crystallography. TheP‐phosphanylphosphaalkene (Me3Si)2C=PP[C(SiCl2F)(SiMe3)2]SiCl2F (8a) was detected in the reaction mixtures by31P NMR spectroscopy, accompanied by its isomer8b, presumably (Cl2FSi)(Me3Si)C=PP[C(SiCl2F)(SiMe3)2]SiMe3. The unsymmetric dimers8aand8brearrange by a 1,3‐(P→C) silyl group shift, providing the inversion‐symmetric diphosphene6. Compound6was transformed with selenium into a selenadiphosphirane (9). Quantum chemical calculations were performed on intermediates on the route from1and2to the metastable unsymmetric dimers8aand8b. The addition of SiCl2to the P=C bond of1, followed by ring opening of the silaphosphirane4, provides the phosphinidene (Me3Si)2(Cl2FSi)CP (5), which rearranges further to isomericP‐silylphosphaalkenes (Me3Si)2C=PSiCl2F (7a) and (Cl2FSi)(Me3Si)C=PSiMe3(7b). Rapid phosphinidene–phosphaalkene P–P coupling reactions of5with7aand with7bfollowed by 1,2‐(P→P) silyl group shift of ylide‐type dimers11aand11bexplain the formation of the observed species8aand8b. The absence of species related to8bin previous experiments on the reactions of theP‐chlorophosphaalkene (Me3Si)2C=PCl (1′) with Si2Cl6, with Me3GeSiCl3, and with Me3SiSiCl3, allows us to suggest that in theP‐chlorophosphaalkene case nucleophile‐supported SiCl2insertion into the P–Cl bond or the substitutive Cl–/SiCl3–exchange are the preferred routes to the metastableP‐(trichlorosilyl)phosphaalkene (Me3Si)2C=PSiCl3.