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Borole/Borapyramidane Relationship
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DOI：10.1021/jacs.2c01727.png)
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Abstract
En 中文
Boroles and borapyramidanes are classical and nonclassicalconstitutional isomers, respectively. It is here shown that they can indeed beinterconverted. Treatment of the bis(alkynyl)B(C6F5) SMe2adduct3middotSMe2withHB(C6F5)2gave borole1middotSMe2, featuring trimethylsilyl substituents in both alpha positions to boron, by means of a 1,1-hydroboration/alkenylboration sequence.Photolysis of the classical borole adduct1middotSMe2resulted in rearrangement to its nonclassical structural isomer, borapyramidane2,inhigh yield, which exhibits a vicinal pair of trimethylsilyl substituents at the square pyramidane base. Neutral borapyramidane2is arare example of an isoster of the (CH)5+pyramidane cation. Thermolysis of borapyramidane2in the presence of SMe2at 60 degrees C re-formed borole1middotSMe2, which converted at 100 degrees C to 2,3-bis-silyl-substituted borole isomer8middotSMe2. Its photolysis also gaveborapyramidane2. Prolonged photolysis of2at elevated temperatures converted this to borapyramidane isomer10containing a pairof trimethylsilyl groups in 1,3-position at its square C4-pyramidal base. The borole and borapyramidane isomers were characterizedby X-ray diffraction, and the system was analyzed by density functional theory (DFT) calculations.
Keywords:
(CH)5+
HYDROBORATION
BOROLES
BORANE
Journal
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15.6
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20.0W
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60.2W