We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
Formation and X-ray structure of the host–guest adduct [Pd<sub>3</sub>(dppm)<sub>3</sub>(CO)(NO<sub>3</sub>)]<sup>+</sup> and the mechanism of its electrochemical reduction.
- Authors
Brevet, David; Lucas, Dominique; Richard, Philippe; Vallat, Alain; Mugnier, Yves; Harvey, Pierre D.
- Abstract
[Pd3(dppm)3(CO)]2+, [Pd3]2+, reacts with NO3– to form the host–guest adduct [Pd3(dppm)3(CO)(NO3)]+, [Pd3(NO3)]+. The presence of NO3– inside the cavity is confirmed by X-ray crystallography. Using a qualitative relationship between λmax (UV–vis) and the association constant of various adducts, the relative binding between NO3– and [Pd3]2+ is in the same order of magnitude of that between CF3CO2– and [Pd3]2+. Based on Pd···O distances, the NO3– ion is relativity more weakly associated to [Pd3]2+ in comparison with the known [Pd3(CF3CO2)]+. Using variation of [NO3–] in the presence of [Pd3](PF6)2 and variation of scan rates, the resulting cyclic voltammogramms (CV) were simulated to extract both kinetic and thermodynamic constants associated to a square scheme. Both the anodic and cathodic scans of the title cluster exhibits ECE mechanisms (E = electrochemical process; C = chemical process). For the anodic scan, the EEC event is not ruled out, at least as a minor process.
- Subjects
ELECTROLYTIC reduction; NITRATES; PALLADIUM; ELECTROCHEMISTRY; THERMODYNAMICS
- Publication
Canadian Journal of Chemistry, 2006, Vol 84, Issue 2, p243
- ISSN
0008-4042
- Publication type
Article
- DOI
10.1139/V05-249