On the mechanism of racemisation of dichlorobis(ethylenediamine)-metal chlorides [metal = cobalt(III) or chromium(III)] in the solid state |
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| Authors: | D Banerjea J C Bailar Jr |
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| Institution: | (1) Department of Chemistry, Inorganic Chemistry Division, University College of Science, 92 Acharya Prafulla Chandra Road, 700009 Calcutta, India;(2) Department of Chemistry, University of Illinois, 61801 Urbana, Il., USA |
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| Abstract: | Summary In the solid state l-cis-M(en)2Cl2]Cl M=cobalt(III) or chromium(III)] undergoes thermal racemisation smoothly at 158 °C without anycis-trans interconversion. The values of krac,  H and S are 6 × 10–6s–1, 218 kJM–1 and 156.1 JK–1M–1 for the cobalt(III) complex and 3.5 × 10–5s–1, 229.7 kJM–1 and 197.9 JK–1M–1 for the chromium(III) complex, respectively. The results are only in accord with a rhombic twist mechanism of the type originally proposed by Ray and Dutt for M(AA)3] complexes. |
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