Ligand assembly and metal ion complexation: synthesis and X-ray structure of Ni(II) and Cu(II) benzoate and 4-tert-butylbenzoate complexes of cyclam

Lindoy, Leonard F., Mahinay, Myrna S., Skelton, Brian W., and White, Allan H. (2003) Ligand assembly and metal ion complexation: synthesis and X-ray structure of Ni(II) and Cu(II) benzoate and 4-tert-butylbenzoate complexes of cyclam. Journal of Coordination Chemistry, 56 (14). pp. 1203-1213.

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Abstract

The syntheses and X-ray structures of trans-[Ni(O-benzoato)2(cyclam)], trans-[Cu(H2O)2(cyclam)]-(benzoate)2·2H2O and trans-[Cu(H2O)2(cyclam)](4-t-butyl-benzoate)2 (where cyclam is 1,4,8,11-tetraazacyclotetradecane) are described. The nickel complex has a tetragonally distorted octahedral coordination geometry with cyclam occupying the equatorial plane in a stable trans-III arrangement, with benzoate ligands filling the axial positions. The structure closely resembles the arrangement in the previously described hydrogen-bonded (metal-free) ligand assembly [(cyclamH2)·(4-t-butyl benzoate)2]·2(benzoic acid) if the latter benzoic acid moieties, which do not interact directly with the cyclam moiety, are ignored. The 2 : 1 fragment thus may be viewed as a ligand assembly “preorganized” for nickel ion complexation. In contrast to the nickel structure, the two trans-axial sites in both copper structures are occupied by aqua rather than O-carboxylate ligands. Although they do not form part of the inner coordination sphere in either complex, the two carboxylate anions remain hydrogen bound to the (coordinated) cyclam ligand, with the mode of packing being generally similar in each complex.

Item ID: 13773
Item Type: Article (Refereed Research - C1)
Keywords: copper; macrocycle; metal ion complexation; nickel
ISSN: 1029-0389
Date Deposited: 04 Nov 2010 02:41
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
Citation Count from Web of Science Web of Science 10
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