
%0 Journal Article
%A Buckingham, DA 
%A Clark, CR 
%A Liddell, GF 
%A Simpson, J 
%T The Thermal Isomerization of Coordinated Thiocyanate in Crystalline <I>trans</I>-[Co(NH<sub>3</sub>)<sub>4</sub>(<sup>15</sup>NH<sub>3</sub>)SCN](N<sup>14</sup>CS)<sub>2</sub>
%J Australian Journal of Chemistry
%D 1993/04/01
%V 46
%N 4
%P 503-527
%K 
%R https://doi.org/10.1071/CH9930503
%U https://www.publish.csiro.au/paper/CH9930503 
%X Heating crystalline trans-[Co(NH3)4(15NH3)SCN](N14CS)2 in the dark at c. 60&#176;C results in the following immediate products (partial formulae are shown): 39% trans-CoNCS2+ (without incorporation of ionic thiocyanate ), 31% cis-CoS14CN2+ and 30% cis-CoN14CS2+ (with incorporation of ionic thiocyanate ). A crystal structure of the unlabelled reactant [Co(NH3)5SCN](NCS)2 [a 14.001(5), b 14.176(5), c 14.774(5) &#506;, &#946; 117.12(3)&#176;, P21/n, Z = 8, 2898 reflections with I > 2&#963;(I), R 3.85%, Rw 4.10%] identifies two independent cobalt(III) cations in the asymmetric unit, and a consideration of the four distinct lattice thiocyanates identifies one of these, S(4)C(4)N(4)-, as that most likely to be involved in replacing the originally coordinated SCN-; S(4) at Co(1), and N(4) at Co(2). Intramolecular (as distinct from intermolecular) isomerization of coordinated thiocyanate is suggested for the formation of trans-CoNCS2+. The solid-state incorporation of lattice N14CS- and S14CN- is compared to that found in aqueous solution where ion-paired N14CS- and S14CN- as well as H2O compete in a solvent-cage, intramolecular , exchange process. The structure of the coordination isomer [Co(NH3)5NCS]SO4.1.5H2O, containing the product CoNCS2+ cation [a 6.621(9), b 7.123(21), c 26.906(19) &#506;, Pnma, Z = 4,524 reflections with I > 2&#963;(1), R 6.34%, Rw 7.67%], is reported. A reexamination of the crystal structure of [Co(NH3)5SCN]Cl2.H2O (ref. 1) suggests that hydrogen bonding to ammine ligands, rather than a more open structure or poorer positioning of lattice Cl-, is the reason for the non-incorporation of ionic Cl- on heating this material. 
