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Silicon analogues of bicyclo[1.1.0]butanes are known to exhibit a bond stretch isomerism where the bridgehead SiSi bond changes in both length and geometry. The bridgehead silicon atom of long bond (lb) isomers exhibits an unusual geometry where all the bonds are located on the same hemisphere, making the geometry of the bridgehead SiSi bond the so‐called inverted σ bond in contrast with the typical...
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