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‐C 6 H‐2,3,4‐(OCH 3 ) 3 ‐6‐(CHN)} 2 ‐CH 2 –CH 2 ] 2 ( 15 ), [Hg‐{1‐C 6 H‐2,3,4‐(OCH 3 ) 3 ‐6‐(CHN)} 2 ‐C 6 H 10 ] 2 ( 16 ) and [Hg‐{1‐C 6 H‐2,3,4‐(OCH 3 ) 3 ‐6‐(CHN)} 2 ‐C 6 H 4 ] 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· Cu]ClO 4 ) and 26 ([ 16· Cu]ClO 4 ), were obtained upon the treatment of [Cu(CH 3 CN) 4 ClO 4 ] with macrocycles 15 and 16 , respectively. Similarly, brown colored Ag I complexes, 25 ([ 15· Ag]ClO 4 ), and 27 ([ 16· Ag]ClO 4 ) were isolated by reacting macrocycles 15 and 16 with AgClO 4 . The reaction of macrocycle 15 with equimolar Pt(COD)Cl 2 afforded cyclometalated platinum(II) complex, Pt‐{1‐C 6 H‐2,3,4‐(OCH 3 ) 3 ‐6‐(CHN‐CH 2 )} 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 d 10 ··· d 10 interactions as well as d 10 ··· d 8 interactions in the synthesized compounds.