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By Cotton F.A., Wilkinson G.

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Rate Constants and Thermodynamic Parameters for Reactions between Metal Ion Complexes at 25°C 8 8 8 8 8 8 8 8 8 8 100 100 1 2 2 2 2 2 2 3 5 5 6 6 6 Ref. V. 2 -36 -30 -29 7 7 7 8 8 8 8 8 8 8 9 9 9 100 100 100 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 0- I\J [Cr(NH3ls(p-ABbenzaldehyde)]2+ [Cr(NH3ls(p-ABsalicylaldehyde) f+ [Cr(NH 3)s(p-ABvanillin)]2+ [Co(NH 3)4(glycine)]2+ + Cr2+ [Co(NH 3)4(D,L-alanine)f+ + Cr2+ [Co(NH3)4(D,L-phenylalanine)f+ + Cr2+ [Co(EDTA)r + Cr2+ [Co(HEDTA)(OH2)] + Cr 2+ [Co(HEDTA)CIr + Cr 2+ [Co(NH3)S02CCH2NCsH4CONH2]3+ + Cr2+ [Co(NH3)S02CCH202CCs~NH]3+ + Cr 2+ [Co(NH3ls02(CH2h02CCsH4NH]3+ + Cr 2+ [Cr(NH3ls(p-ABH) ]3+ [Co(NH3)sNC(CH 2hCN] + Cr2+ [Co(NH 3lsNCCH 2CONH 2] + Cr2+ [Co(NH 3)sNCCH 2C0 2CH 3] + Cr2+ [Co(NH 3lsNCCH 2C0 2r + Cr2+ [Cr(NH3ls(o-ABH)]3+ + Cr2+ [Cr(NH 3ls(o-AB)]2+ + Cr2+ [Cr(NH3ls(o-ABbenzaldehyde)f+ + Cr2+ [Cr(NH 3)s(o-ABsalicylaldehyde) f+ [Cr(NH 3)s(o-ABvanillin)]2+ [Cr(NH 3)s(m-ABH)]3+ [Cr(NH 3)s(m-ABbenzldehyde)]2+ [Cr(NH3)s(m-ABsalicylaldehyde)f+ [Cr(NH 3)s(m-ABvanillin)]2+ Chromium(II)-contd.

With Hg2+, electron transfer occurs with a number of hydroxyalkyls but with the -CH20H and -CH20CH3 derivatives, an electrophilic substitution resulting in the organomercurial is noted. 4. (20) Iron(III) inhibits the reaction suggesting participation by TI(II). An inner-sphere halide bridged mechanism is proposed(21) for the Fe2+ reduction of trans-[Co(DH)zpyX] where DH- is dimethylglyoximate anion and X is the halogen ion. Rate constants for both uncatalyzed and base-catalyzed pathways show an increase in the order 38 2 • Reactions between Metal Complexes Cl- < Br- < r.

Assumed. f Second-order rate constant (M-I S-I) from application of the Marcus cross relation. , Second-order rate constant (M 1 s '). H 8 for the thermal electron transfer reaction. 1 M NaOAc (HOAc buffer). I Polyvanadic acid gel. m A previously reported IT band is not confirmed. ~- yV ... 9 X X X 10 12d 10 -5g 106d 80 81 116 53 53 53 107 (ef. 53) 56 ..... ~. v, ..... '".... ~ ;:: ~ ~ ;:: ~ <"> ~ e.. '"~ ~ l:>... ;:: ~ e.. ~ • ~ 1 • General and Theoretical 16 ligand, and the final metal-to-metal electron transfer is too rapid to follow.

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