Trans effect Transferases

DNA polymerases, 5, 1007 Trans effect, 1,16, 26, 315 metal complexes, 2, 705, palladium(II) amine complexes, 5, 1115 platinum complexes, 5, 353, 493 six-coordinate compounds. 1, 49 T ransestcrification metal alkoxide synthesis, 2, 340 Transferases zinc, S, 1002... 

Iersel ML, Ploemen JP, Struik I, van Amersfoort C, Keyzer AE, Schefferlie JG, van Bladeren PJ. 1996. Inhibition of glutathione S-transferase activity in human melanoma cells by alpha,beta-unsaturated carbonyl derivatives. Effects of acrolein, cinnamaldehyde, citral, crotonaldehyde, curcumin, ethacrynic acid, and trans-2-hexenal. Chem Biol Interact 102 117-132. 

The exact value depends slightly on a variety of conditions, including the identity of the trans axial ligand—so-called base-on or base-off forms—and the solvent, which results in considerable radical-cage effects. These issues are outlined in detail in Section 8.25.3.1. In contrast, the BDE for methyl B12 is approx. 155kJmoD The higher value is apparently sufficient to preclude cobalt-carbon homolysis in methylcobalamin-mediated reactions, and to allow for the heterolytic pathway to operate in methyl transferases. 

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