
%0 Journal Article
%A Healy, PC 
%A Connor, JW 
%A Skelton, BW 
%A White, AH 
%T Alkyl Substituent Effects in Diamagnetic Dithiocarbamate Cobalt(III) and Nickel(II) Complexes
%J Australian Journal of Chemistry
%D 1990/06/01
%V 43
%N 6
%P 1083-1095
%K 
%R https://doi.org/10.1071/CH9901083
%U https://www.publish.csiro.au/paper/CH9901083 
%X Single-crystal X-ray structure determinations have been recorded at 295 K for the tris(dithiocarbamato)cobalt(III) compounds: [Co(S2CN(CH2)4)3], [Co(S2CNEt2)3] (redeterminations), [Co(S2CN(CH2Ph)2)3], and [Co(S2CNPri2)3] at 120 and 295 K. [Co(S2CN(CH2)4)3] crystallizes in the space group C2/c with a 28.984(15), b 14.416(2), c 16.206(15)&#506;, &#946; 104.20(5)&#176;, Z 12; [Co(S2CNEt2)3] also crystallizes in space group C2/c with a 14.097(3), b 10.305(2), c 17.070(7)&#506;, &#946; 110.19(3)&#176;, Z 4; [Co(S2CN(CH2Ph)2)3] crystallizes in space group P21 with a 11.851(6), b 29.920(8), c 12.395(3)&#506;, &#946; 97.74(4)&#176;; [Co(S2CNPri2)3] crystallizes in space group R3c with a 13.367(6)&#506;, &#945; 58.04(2)&#176; (295 K); a 13.155(6)&#506;, &#945; 58.59(3)&#176; (120 K), Z 2. The structure of [Ni(S2CNPri2)2] has been redetermined, the complex crystallizing in the space group P21/c with a 8.147(2), b 17.820(3), c 15.630(3)&#506;, &#946; 110.32(2)&#176;, Z 4. The results obtained from this study support the hypothesis, put forward by Ymen and Stahl, that the influence of aliphatic hydrocarbon substituents on the ligand-field strength at the sulfur atoms of the dithiocarbamate ligand is not through the &#960; bonding network of the conjugated S2CN moiety, but, rather, intraligand S&#8230;H-C interactions which increase with increasing bulk of the substituent atoms. Unlike the free anion systems, or the iron(III) complexes, however, the changes in the S-C-S angles with increasing field strength, while observable, are very small. 
