Intermetallic Bonds in Metallophilic Mercuraazametallamacrocycles of Synthetic Design

详细信息    查看全文

• 作者：Upali Patel ; Sagar Sharma ; Harkesh B. Singh ; Sandip Dey ; Vimal K. Jain ; Gotthelf Wolmershuser ; Ray J. Butcher
• 刊名：Organometallics
• 出版年：2010
• 出版时间：October 11, 2010
• 年：2010
• 卷：29
• 期：19
• 页码：4265-4275
• 全文大小：1150K
• 年卷期：v.29,no.19(October 11, 2010)
• ISSN：1520-6041

文摘

22-Membered mercuraazametallamacrocycles 6, 7, and 12 have been synthesized by dipodal condensation (2 + 2) of bis(o-formylphenyl)mercury (11) and 1,2-disubstituted amines. Reduction of macrocycle 6 with sodium borohydride afforded novel 11-membered mercuraazametallamacrocycle 13. Macrocycle 6, when treated with [Cu(CH₃CN)₄]ClO₄ and Cu(OCOCH₃)₂/NH₄PF₆, formed orange-colored Cu^I complexes 14 ([6·Cu]ClO₄) and 15 ([6·Cu]PF₆), respectively, whereas red-colored complex 16 ([12·Cu]ClO₄) was obtained from the reaction of 12 with [Cu(CH₃CN)₄]ClO₄. Similarly, complexes 17 ([6·Ag]ClO₄) and 18 ([6·Ag]PF₆) were synthesized by the reaction of 6 with the corresponding silver salts. The reaction of 6 with Hg(OCOCH₃)₂/NH₄PF₆ led to the formation of hydroxo-bridged complex 19. The reaction of macrocycle 7 with Pd(C₆H₅CN)₂Cl₂ gave access to novel complex 9a. The macrocycles and the complexes have been characterized by elemental analysis, NMR (¹H, ¹³C, ¹⁹⁹Hg), fluorescence spectroscopy, and cyclic voltammetry. The molecular structures of organomercury precursors Hg{1-C₆H₄-2-(CH₂OH)}₂ (10) and Hg{1-C₆H₄-2-(CHO)}₂ (11) and macrocycles 6, 7, and 12 show almost linear geometry around mercury; however, 13 shows a bent structure, i.e., significant deviation of the C−Hg−C angle from linearity. 22-Membered mercuraazametallamacrocycles 6, 7, and 12 are stabilized by secondary Hg···N intramolecular interaction and have an “hour-glass”-like conformation. The molecular structures of 14, 17, and 9a showed metallophilic interactions. The metal ions (Cu^I and Ag^I) are coordinated not only to the four nitrogens but also to two mercury atoms, forming a distorted octahedral geometry around the metal ions.