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We report the regiodivergent reaction of phenylacetylene with a selection of disilenes Tip2Si=SiTipR as well as bridged tetrasiladienes Tip2Si=SiTip−LU−SiTip=SiTip2 (Tip=2,4,6‐iPr3C6H2, R=aryl groups; LU=arylene linkers). The regioselectivity of the [2+2] cycloaddition as determined by NMR spectroscopy and X‐ray crystallography is shown to strongly depend on the nature of the substituent R. The small...
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