Zinc(II), copper(II), and copper(I) complexes of the pentadentate ligand, ((5-MeimidH)$\sb2$DAP) were prepared and studied as their (BF$\sb4$)$\sp-$ salts. The divalent compounds, (M$\sp{\rm II}$((5-MeimidH)$\sb2$DAP)) (BF$\sb4$)$\sb2$ (M = Zn, Cu), were found to have intermediate geometries between idealized trigonal bipyramidal and square pyramidal structures by x-ray crystallography. It is assumed that (Cu$\sp{\rm I}$((5-MeimidH)$\sb2$DAP)) (BF$\sb4$) is also pentacoordinate as is its parent compound, (Cu$\sp{\rm I}$((imidH)$\sb2$DAP)) (BF$\sb4$). In addition to the x-ray structures, the new compounds have been fully characterized, where appropriate, by a battery of techniques for both the solid and solution states. These studies all suggest that the pentacoordinate structures of the solid state are also retained in solution. Variable-temperature proton NMR studies in non-aqueous solvents were used to extensively probe the intramolecular conformational dynamics of (M((5-MeimidH)$\sb2$DAP)) $\sp{\rm n+}$ (M = Zn(II), Cu(I)) and two related pentacoordinate systems ((M((imidH)$\sb2$DAP)) $\sp{\rm n+}$ and (M((py)$\sb2$DAP)) $\sp{\rm {n+}}$). Computer simulation of the temperature-dependent methylene proton regions were used to observe $\lambda$ and $\delta$ chelate ring conformations. Coalesence rate constants were obtained in four of the six cases. The electron self-exchange rate of the (Cu((5-MeimidH)$\sb2$DAP)) $\sp{+/2+}$ couple was measured in CD$\sb3$CN, as a function of temperature, by dynamic NMR line-broadening techniques. Under controlled conditions ($\mu$ = 25 mM), the observed rate constant ranged from 0.9($\pm$0.1) $\times$ 10$\sp4$ M$\sp{-1}$ s$\sp{-1}$ (243 K) to 3.9($\pm$0.4) $\times$ 10$\sp4$ M$\sp{-1}$ s$\sp{-1}$ (293 K) with activation parameters of $\Delta$H$\sp\ddagger$ = 12.5 kJ mol$\sp{-1}$ and $\Delta$S$\sp\ddagger$ = $-$116 J mol$\sp{-1}$ K$\sp{-1}$. The present electron self-exchange rate constant, together with those for two related Cu(I/II) couples ((Cu((imidH)$\sb2$DAP)) $\sp{+/2+}$ and (Cu((py)$\sb2$DAP)) $\sp{+/2+}$) indicate a possible relationship between intramolecular dynamics of the Cu(I) species and the electron self-exchange rates of the Cu(I/II) couples. Finally, the reactivity of (Cu$\sp{\rm I}$((5-MeimidH)$\sb2$DAP)) $\sp+$ towards O$\sb2$ was investigated and found to be something other than a reversible process. Although an initial uptake stoichiometry of 2Cu:O$\sb2$ was obtained by manometry, a Toepler pump experiment showed that regeneration of Cu(I) proceeded without significant release of O$\sb2$.
| Identifer | oai:union.ndltd.org:RICE/oai:scholarship.rice.edu:1911/16333 |
| Date | January 1990 |
| Creators | Coggin, DeAnna Kay |
| Contributors | Wilson, Lon J. |
| Source Sets | Rice University |
| Language | English |
| Detected Language | English |
| Type | Thesis, Text |
| Format | 258 p., application/pdf |
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