Electron self-exchange kinetics in two average-valence dicopper cryptates.
Electron self-exchange rates, reported for two average-valence dicopper cryptates are, at around 10(5) M-1 s-1, at the high end of the range for small-molecule model compounds. The cross-exchange reaction rate, and those for oxidation with [Co(ox)3]3-, are consistent with an outer-sphere reaction mechanism. Despite the necessity for copper-copper bond making and breaking in the course of redox for one of the cryptates, the self-exchange rate is not decreased relative to the other cryptate, showing that this step is not rate limiting.
Coyle
J L
JL
School of Chemistry, Queens University Belfast, Belfast BT9 5AG, UK.
Elias
H
H
Herlinger
E
E
Lange
J
J
Nelson
J
J
D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D004583:Electrons; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D009942:Organometallic Compounds / Q000737:chemistry*
D019086:Bridged Bicyclo Compounds, Heterocyclic; D009942:Organometallic Compounds