UNSPECIFIED (2001) trans-dioxocyclam (1,4,8,11-tetraazacyclotetradecane-2,9-dione) dihydrate and its Ni-II complex. ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 57 (Part 4). pp. 359-362. ISSN 0108-2701

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Abstract

The crystal structures are reported of trans-dioxocyclam dihydrate, C10H20N4O2. 2H(2)O, a structural isomer of the well known cis-dioxocyclam, and of its novel Ni complex, (1,4,8,-11-tetraazacyclotetradecane-2,9-dionato-kappa N-4)nickel(II) dihydrate, [Ni(C10H18N4O2)]. 2H(2) O, the first example of a transition metal complex of this ligand. Both molecules lie on crystallographic centres of inversion. The free ligand has two of its N atoms turned outwards from the ring and hydrogen bonded to water molecules. A major conformational change takes place in the complex in which the ligand binds in a trans tetradentate fashion, as suggested by the electronic spectrum. The nickel(II) ion is low spin, although the electronic spectrum of the complex in water indicates an equilibrium mixture of low-spin and high-spin species. The irreversible electrochemical oxidation of [NiL1] (L-1 is deprotonated transdioxocyclam, C10H18N4O2) in water occurs at a potential of 0.964 V [versus SHE (standard hydrogen electrode)], which is very similar to that for the Ni-cis-dioxocyclam complex.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Journal or Publication Title:	ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS
Publisher:	MUNKSGAARD INT PUBL LTD
ISSN:	0108-2701
Date:	15 April 2001
Volume:	57
Number:	Part 4
Number of Pages:	4
Page Range:	pp. 359-362
Publication Status:	Published
URI:	http://wrap.warwick.ac.uk/id/eprint/12274

Data sourced from Thomson Reuters' Web of Knowledge

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