185898-05-9Relevant academic research and scientific papers
A convenient high yield synthesis of 2,2′:6′,2″:6″,2?:6?,2″″: 6″″,2″?-sexipyridine and helical transition-metal complexes of substituted sexipyridines
Chotalia, Rohit,Constable, Edwin C.,Neuburger, Markus,Smith, Diane R.,Zehnder, Margareta
, p. 4207 - 4216 (1996)
The compound 2,2′:6′,2″:6″,2?:6?,2″″: 6″″,2″?-sexipyridine (spy) has been synthesised in high yield by the coupling of 6-bromo-2,2′:6′,2″-terpyridine with a nickel(0) reagent, followed by demetallation of the resultant double-helical [Ni2(spy)2]4+ complex with KCN. In order to probe the effects of substitution of spy upon helication processes, the substituted compounds 4′,4″″-bis(methylsulfanyl)-2,2′:6′,2″: 6″,2?:6?,2″″:6″″,2″?- sexipyridine (msspy), 4′,4″″-diphenyl-2,2′:6′,2″:6″, 2?:6?,2″″:6″″,2″?- sexipyridine (pspy) and 4′,4″″-bis(4-tert-butylphenyl)-2,2′:6′,2″: 6″,2?:6?,2″″:6″″,2″?- sexipyridine (tbspy) were also prepared and studied. The reaction of each of these compounds with transition-metal ions capable of adopting an octahedral geometry results in the self-assembly of dinuclear double-helical complexes of the type [M2L2]4+ [M = iron(II), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) or mercury(II); L = spy, msspy, pspy or tbspy]; the double-helical topology of the zinc complex of pspy was confirmed by a crystal-structure analysis of the salt [Zn2(pspy)2]-[PF6] 4-2MeCN·2H2O [space group P42212, a = 15.518(2), c = 18.443(1) A, R = 0.0638, R′ = 0.0735].
