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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Alkyl Substituent Effects in Diamagnetic Dithiocarbamate Cobalt(III) and Nickel(II) Complexes

PC Healy, JW Connor, BW Skelton and AH White

Australian Journal of Chemistry 43(6) 1083 - 1095
Published: 1990

Abstract

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)Ǻ, β 104.20(5)°, 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)Ǻ, β 110.19(3)°, 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)Ǻ, β 97.74(4)°; [Co(S2CNPri2)3] crystallizes in space group R3c with a 13.367(6)Ǻ, α 58.04(2)° (295 K); a 13.155(6)Ǻ, α 58.59(3)° (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)Ǻ, β 110.32(2)°, 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 π bonding network of the conjugated S2CN moiety, but, rather, intraligand S…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.

https://doi.org/10.1071/CH9901083

© CSIRO 1990

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