Ortho-mercurated [({N-methyl-N-arylamino}methyl)ferrocenes] and their transpalladation. Crystal structures of [(η5-C5H5)Fe{η5-C5H3(HgCl)CH2N(CH3)C6H4OCH3-4}]2, [(η5-C5H5)Fe{η5-C5H3(HgCl)CH2N(CH3)C6H4Cl-3}] and [(η5-C5H4HgCl)Fe{η5-C5H4CH2N(CH3)C6H4Cl-4}]

Treatment of ferrocenylamines [(η5-C5H5)Fe{η5-C5H4CH2N(CH3)C6H4R}] (4) (R = 4-MeO (a), 4-Me (b),  H (c),  4-Cl (d),  3-Cl (e),  3-NO2(f)) with mercury (II) acetate and lithium chloride yielded ortho-mercurated [(η5-C5H5)Fe{η5-C5H3(HgCl)CH2N(CH3)C6H4R}] (6) (R = same as before) and a minor product [(η5-C5H4HgCl)Fe{η5-C5H4CH2N(CH3)C6H4Cl-4}] (7) from 4d (R = 4-Cl). The character of the substituents on the phenyl rings might play an important role in governing the product distributions. The preference of intermolecular over intramolecular N–Hg interactions in 6 was observed and rationalized. Transpalladations of 6via disodium tetrachloropalladate (II) gave the corresponding cyclopalladated complexes in low yields. The molecular structures of 6a, e, and 7 were determined by single crystal X-ray analysis.

Graphical abstractTreatment of ferrocenylamines [(η5-C5H5)Fe(η5-C5H4CH2N(CH3)C6H4-R)] (4) with Hg(OAc)2/LiCl resulted in predominately the ortho-mercurated complexes 6. The preferable intermolecular over intramolecular N–Hg interaction was observed and rationalized. Transpalladation of 6 gave the cyclopalladated complexes in low yields. The structures of 6a, e, and 7 were determined by X-ray single crystal diffraction.Figure optionsDownload full-size imageDownload as PowerPoint slide