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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 23, Number 1
BKCSDE 23(1)
January 20, 2002 

Synthesis of a Di-N-cyanoethylated Tetraaza Macrocycle Containing Eight C-Methyl Groups and Its Nickel(II) Complex: Effects of the Methyl Groups on Their Properties
Shin-Geol Kang, Kiseok Ryu, Jinkwon Kim
Macrocyclic compounds, Nickel(II) complexes, Cyanoethyl pendant arms, Crystal structure.
A new di-N-cyanoethylated 14-membered tetraaza macrocycle 1,8-bis(2-cyanoethyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane (L2 ) and its nickel(Ⅱ) complex [NiL2(OAc)]+ have been prepared. The square-planar complex [NiL2 ](ClO4)2 can be prepared by addition of HClO4 to a hot aqueous solution of [NiL2 (OAc)]+ . The Ni-N (tertiary amino group) bond distances (2.008Å) of [NiL2](ClO4)2 are relatively long, and the complex exhibits a d-d transition band at unusually long wavelength (ca. 515 nm). The complex [NiL2 ](ClO4)2 rapidly reacts with acetate ion or ethylenediamine (en) to produce [NiL2(OAc)]+ or [Ni(en)3]2+ , respectively, and is readily decomposed in NaOH (0.01 M) solution. The chemical properties of [NiL2]2+ as well as its synthetic procedure are quite different from those for other related 14-membered tetraaza macrocyclic complexes. Effects of the N-cyanoethyl and C-methyl groups on the properties of L2
81 - 85
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