
%0 Journal Article
%A Lawrance, GA 
%A Martinez, M 
%A Skelton, BW 
%A White, AH 
%T Quinquedentate Coordination of 6-Methyl-1,11-dithia-4,8-diazacyclotetradecan-6-amine to Cobalt(III). X-Ray Crystal Structure of the [Co(N<sub>3</sub>S<sub>2</sub>)(OOCCH<sub>3</sub>)] (ClO<sub>4</sub>)<sub>2</sub>.H<sub>2</sub>O Complex
%J Australian Journal of Chemistry
%D 1991/01/01
%V 44
%N 1
%P 113-121
%K 
%R https://doi.org/10.1071/CH9910113
%U https://www.publish.csiro.au/paper/CH9910113 
%X The pendant arm macrocycle 6-methyl-1,11-dithia-4,8-diazacyclotetradecan-6-amine (7) can coordinate to cobalt(III) as a quinquedentate N3S2 ligand . Spectroscopy indicated a geometry with the macrocycle folded and the pendant amine and the unidentate donor in cis dispositions for the [Co(7) Cl ]2+ and [Co(7)(OOCCH3)]2+ products isolated. An X-ray crystal structure analysis of [Co(7)(OOCCH3)](ClO4)2.H2O characterized the cis stereochemistry. The complex crystallized in the Pbca space group, a 10.620(9), b 13.926(9), c 32.35(2)&#506;, and analysis defined a distorted octahedral geometry with the primary and two secondary nitrogen donors occupying an octahedral face with relatively short Co-N bonds [1.937(7)-1.950(7)&#506;], the acetate ion [Co-O 1.905(6)&#506;] trans to one of the secondary amine donors and thioether donors [Co-S 2.223(3), 2.227(3)&#506;] trans to the other nitrogen donors. Significant angle distortions occur around the metal ion. Base hydrolysis of the chloro complex is slow and stereoretentive , with a rate constant of 1.08&#215;103 dm3 mol-1 s-1 at 25&#176;C, 15-fold faster than for the pentaaza analogue. 
