Metallophilic Mercuraazamacrocycles Derived from Bis{6-formyl-(2,3,4-trimethoxy)phenyl}mercury: Reactivity with d(10) and d(8) Metal Ions

A (2+2) Dipodal condensation of bis{6-formyl-(2,3,4-trimethoxy)phenyl}mercury (14) with various 1,2-disubstitued diamines e.g., ethylenediamine, trans-1,2-diaminocyclohexane and o-phenylenediamine led to the formation of 22-membered mercuraazametallamacrocycles, [Hg-{1-C6H-2,3,4-(OCH3)(3)-6-(CHN)}(2)-CH2-CH2](2) (15), [Hg-{1-C6H-2,3,4-(OCH3)(3)-6-(CHN)}(2)-C6H10](2) (16) and [Hg-{1-C6H-2,3,4-(OCH3)(3)-6-(CHN)}(2)-C6H4](2) (17) respectively. The acceptor abilities and reactivities of the macrocycles are compared with the corresponding 22-membered mercuraazametallamacrocycles obtained from the condensation of bis(formylphenyl)mercury (12) with the diamines. Also attempts have been made to prepare macrocycles with functionalized aryldiamines. Orange colored Cu-I complexes, 24 ([15 center dot Cu]ClO4) and 26 ([16 center dot Cu]ClO4), were obtained upon the treatment of [Cu(CH3CN)(4)ClO4] with macrocycles 15 and 16, respectively. Similarly, brown colored Ag-I complexes, 25 ([15 center dot Ag]ClO4), and 27 ([16 center dot Ag]ClO4) were isolated by reacting macrocycles 15 and 16 with AgClO4. The reaction of macrocycle 15 with equimolar Pt(COD)Cl-2 afforded cyclometalated platinum(II) complex, Pt-{1-C6H-2,3,4-(OCH3)(3)-6-(CHN-CH2)}(2) (28). Bis(2-amino-5-methylphenyl)mercury (23), shows a very strong intermolecular HgHg interaction. Density functional theory calculations and atoms in molecules analysis revealed the presence of metallophilic d(10)center dot center dot center dot d(10) interactions as well as d(10)center dot center dot center dot d(8) interactions in the synthesized compounds