Reversible, Photoinduced Activation of P4 by Low-Coordinate Main Group Compounds

被引:58
作者
Dube, Jonathan W. [1 ,2 ]
Graham, Cameron M. E. [1 ,2 ]
Macdonald, Charles L. B. [3 ]
Brown, Zachary D. [4 ]
Power, Philip P. [4 ]
Ragogna, Paul J. [1 ,2 ]
机构
[1] Univ Western Ontario, Dept Chem, London, ON N6A 5B7, Canada
[2] Univ Western Ontario, CAMBR, London, ON N6A 5B7, Canada
[3] Univ Windsor, Dept Chem & Biochem, Windsor, ON N9B 3P4, Canada
[4] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA
基金
加拿大自然科学与工程研究理事会;
关键词
bond activation; germanium; main group chemistry; reversible reactivity; white phosphorus; P-P BOND; METAL-FREE; WHITE PHOSPHORUS; GROUP ELEMENTS; CARBENE ACTIVATION; CAGE; INSERTION; SILYLENE; HYDROGEN; FUNCTIONALIZATION;
D O I
10.1002/chem.201402031
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Two unique systems based on low-coordinate main group elements that activate P-4 are shown to quantitatively release the phosphorus cage upon short exposure to UV light. This reactivity marks the first reversible reactivity of P-4, and the germanium system can be cycled 5times without appreciable loss in activity. Theoretical calculations reveal that the LUMO is antibonding with respect to the main group element-phosphorus bonds and bonding with respect to reforming the P-4 tetrahedron, providing a rationale for this unprecedented activity, and suggesting that the process is tunable based on the substituents.
引用
收藏
页码:6739 / 6744
页数:6
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