Difunctionalization of primary aromatic amines with ethylene; synthesis of μ-arylnitrilobis(ethane-2,1-diyl)dimercury(II) complexes. Crystal structure of 2,4,6-Me 3C 6H 2N-(CH 2CH 2HgCl) 2

Abstract

Reaction of primary aromatic amines, mercuric acetate, and ethylene in tetrahydrofuran under pressure (ca. 40 atm) yields the organomercurials ArN(CH 2CH 2-HgOAc) 2 (Ar = Ph, 2-ClC 6H 4, 3-ClC 6H 4, or 4-ClC 6H 4) or, after treatment of the crude products with sodium halide, ArN(CH 2CH 2HgX) 2 (Ar = 4-MeC 6H 4, 4-MeOC 6H 4, or 2,4,6-Me 3C 6H 2, X = Cl; Ar = 2,4-Cl 2C 6H 3, 2,6-Cl 2C 6H 3, or 2,4,6-Br 3C 6H 2, X = Br). The X-ray diffraction study of 2,4,6-Me 3C 6H 2N(CH 2CH 2HgCl) 2 shows the molecules to have near linear C-Hg-Cl stereochemistry, and to be arranged in centrosymmetric dimers with weak Hg ··· Cl intermolecular bonding.