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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 21, Number 11
BKCSDE 21(11)
November 20, 2000 

Preparation and Properties of New Di-N-alkylated 14-Membered Tetraaza Macrocycles and Their Nickel(II) and Copper(II) Complexes
Shin-Geol Kang, Jeonghoon Song, Dongmock Whang, Kimoon Kim
New 14-membered tetraaza macrocycles 1,8-diallyl-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane (L²) and 1,8-bis(n-propyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane (L³) have been prepared by direct reaction of 2,5,5,7,9,12,12,14-octamethyl-1,4,8,11-tetraazacyclotetradecane (L¹)with allyl bromide or n-propyl bromide. The nickel(II) and copper(II) complexes of L²and L³have been prepared. The macrocycles show high copper(II) selectivity against nickel(II) ion in methanol solutions containing water. The wavelengths (ca. 505 nm) of the d-d bands for the nickel(II) complexes are extraordinarily longer than those for the complexes of L¹and other related di-N-alkylated 14-membered tetraaza macrocycles. Crystal structure of [NiL²](ClO4)₂ shows that the average Ni-N bond distance (1.992Å) of the complex is distinctly longer than those of other related nickel(II) complexes. Effects of the N- and C-substituents on the properties of the macrocyclic compounds are discussed.
1106 - 1110
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