Indium(III) benzenechalcogenolates (chalcogen = sulfur and selenium) promote the rigorous Markovnikov hydrochalcogenation of terminal alkynes. The generality and limitations of the reaction with aminoalkynes leading to allylic amines bearing vinylic chalcogenide substituents are discussed.
A synthetic route to obtain [p‐H2NC6H4Se]2 (1) in good yield was developed, and the crystal structure of the product was characterized for the first time. The synthesis and structure of the mercury(II) derivative [Hg(SeC6H4NH2)2] (2) was also investigated and is reported herein. The versatile coordination chemistry of [Hg(SeC6H4NH2)2] with halides of the same metal and PCy3 allows the synthesis of [Hg(X)(SeC6H4NH2)(PCy3)] (X = Cl, Br, I) (3–5). The products 1, 3–5 were isolated in crystalline form and characterized by X‐ray structure analysis.
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