科研之友
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摘要
We have reported the mechanistic investigation of the reaction of N2O addition to disilene, trans-[(TMS)(2)N(eta(1)-Me5C5)Si=Si(eta(1)-Me5C5)N(TMS)(2)] (1(t)), employing density functional theory (BP86/TZVP//BP86/SVP) calculations. The potential energy surfaces of the title reaction are broadly classified under three pathways. Pathway I deals with the direct N2O additions to 1(t) affording the transdioxadisiletane ring compound P-t whereas in the same pathway we report a different bifurcation route from intermediate 2(t). This route portrays the isomerization of trans-monooxadisiletane species 2(t) prior to the second N2O addition, finally leading to the cis-isomeric product P-c. Different possibilities for isomerization of disilene 1(t) to 1(c) were studied in pathway II. The cis-disilene (1(c)) formed can subsequently react with two N2O molecules affording the cis-product P. Pathway III details the formation of silanone type intermediate 6, which subsequently combine with another silanone to afford loosely bound intermediates 7 and 8 respectively. The two separated silanone fragments in the isomeric intermediates 7 and 8 can then dimerizes to furnish the desired products. Among all the calculated potential energy surfaces, pathway III remains the most preferred route for disilene oxygenation under normal experimental condition. The present investigation about disilene reactivity will provide a deeper understanding on silylene chemistry and will exhibit promising applicability in main group chemistry as a whole.
- 出版日期2014-6
