0000000000182241
AUTHOR
Ulrich Scholten
Reduction of ferricytochrome c catalyzed by optically active chromium(III) complexes
The reduction rates of horse heart ferricytochrome c by amalgamated zinc or by electrolysis at fixed potential on a mercury pool as the cathode have been measured in a buffered solution at pH 7.5 by absorption spectrophotometry. In both cases, the reaction was strongly accelerated by the presence of the optically active complexes Lambda-[Cr(III)((S,S)-promp)H(2)O](+) (H(2)promp = N,N'-[(pyridine-2,6-diyl)bis(methylene)]-bis[(S)-proline]), Delta-[Cr(III)((R,R)-alamp)H(2)O](+) (H(2)alamp = N,N'-[(pyridine-2,6-diyl)bis(methylene)]-bis[(R)-alanine]) and Lambda-[Cr(III)((S,S)-alamp)(H(2)O)(2)](+). These were shown to undergo reversible one-electron reduction to the corresponding labile chromium(…
The proton complex of a diaza-macropentacycle: structure, slow formation, and chirality induction by ion pairing with the optically active 1,1'-binaphthyl-2,2'-diyl phosphate anion
The protonation of a sterically crowded [N2S6] macropentacycle (1) with 1 equiv of CF3SO3H in CDCl3 is slow and gives the singly (oo(+) [1 x H](+)) and doubly (o(+)o(+) [1 x 2H](2+)) protonated forms as kinetic products, the i(+)o form of [1 x H](+) being the thermodynamic product. i(+)o [1 x H](+) is C3 helically chiral in the solid state and in solution. The barrier to racemization (DeltaG(double dagger)) of the [1 x H](+) propeller is71 kJ mol(-1). The ammonium proton is encapsulated in the tetrahedral coordination sphere provided by the endo (i) nitrogen bridgehead atom and the three proximal thioether sulfurs, which makes [1 x H](+) a proton complex. Use of the optically active acid (R…