“The student can be asked to discuss the factors which affect the equilibrium in DMSO and chloroform solvents 2Co(salen) + 2DMSO + O2 ⇋ [(DMSO)Co(salen)]2O2 Electron donation by a ligand, L, is required to stabilize the structure. Chloroform is a poor donor unlikely to coordinate to cobalt. In DMSO, the high concentration of DMSO provided by the solvent, and the low solubility of the adduct help to force the equilibrium to the right.” Oxygen uptake by a Co(II) Complex T. G. Appleton J. Chem. Ed. 1977, 54, 443
My view: the DMSO alters the HOMO-LUMO properties of the Co(II) such that there is better overlap with the frontier MOs on O2 (a trans influence). O2 bonds to Co at an angle via the π* MOs [Co(III) – O2(-)]
“The student can be asked to discuss the factors which affect the equilibrium in DMSO and chloroform solvents 2Co(salen) + 2DMSO + O2 ⇋ [(DMSO)Co(salen)]2O2 Electron donation by a ligand, L, is required to stabilize the structure. Chloroform is a poor donor unlikely to coordinate to cobalt. In DMSO, the high concentration of DMSO provided by the solvent, and the low solubility of the adduct help to force the equilibrium to the right.” Oxygen uptake by a Co(II) Complex T. G. Appleton J. Chem. Ed. 1977, 54, 443
My view: the DMSO alters the HOMO-LUMO properties of the Co(II) such that there is better overlap with the frontier MOs on O2 (a trans influence). O2 bonds to Co at an angle via the π* MOs [Co(III) – O2(-)]
2Co(salen) + 2DMSO + O2 ⇋ [(DMSO)Co(salen)]2O2
Electron donation by a ligand, L, is required to stabilize the structure. Chloroform is a poor donor unlikely to coordinate to cobalt. In DMSO, the high concentration of DMSO provided by the solvent, and the low solubility of the adduct help to force the equilibrium to the right.”
Oxygen uptake by a Co(II) Complex T. G. Appleton J. Chem. Ed. 1977, 54, 443
My view: the DMSO alters the HOMO-LUMO properties of the Co(II) such that there is better overlap with the frontier MOs on O2 (a trans influence). O2 bonds to Co at an angle via the π* MOs [Co(III) – O2(-)]
2Co(salen) + 2DMSO + O2 ⇋ [(DMSO)Co(salen)]2O2
Electron donation by a ligand, L, is required to stabilize the structure. Chloroform is a poor donor unlikely to coordinate to cobalt. In DMSO, the high concentration of DMSO provided by the solvent, and the low solubility of the adduct help to force the equilibrium to the right.”
Oxygen uptake by a Co(II) Complex T. G. Appleton J. Chem. Ed. 1977, 54, 443
My view: the DMSO alters the HOMO-LUMO properties of the Co(II) such that there is better overlap with the frontier MOs on O2 (a trans influence). O2 bonds to Co at an angle via the π* MOs [Co(III) – O2(-)]
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