Silanethione 2a and silaneselenone 2b—stabilized by intramolecular Si ← N coordination— are obtained as shown below. The X‐ray structure analysis of 2a, 1‐naphthyl instead of phenyl, reveals strong zwitterionic character, which might explain the unexpectedly low reactivity toward nucleophiles and electrophiles (a, X = S; b, X = Se).
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