Metallophilic Mercuraazamacrocycles Derived from Bis{6‐formyl‐(2,3,4‐trimethoxy)phenyl}mercury: Reactivity with d10and d8Metal Ions

Abstract

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 ando‐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 CuIcomplexes,24([15·Cu]ClO4) and26([16·Cu]ClO4), were obtained upon the treatment of [Cu(CH3CN)4ClO4] with macrocycles15and16, respectively. Similarly, brown colored AgIcomplexes,25([15·Ag]ClO4), and27([16·Ag]ClO4) were isolated by reacting macrocycles15and16with AgClO4. The reaction of macrocycle15with equimolar Pt(COD)Cl2afforded 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 Hg···Hg interaction. Density functional theory calculations and atoms in molecules analysis revealed the presence of metallophilic d10···d10interactions as well as d10···d8interactions in the synthesized compounds.