title: A rational basis for the axial ligand effect in C-H oxidation by [MnO(porphyrin)(X)]+ (X = H2O, OH-, O2-) from a DFT study.
abstract: Oxyl radical character in the MnO group of the title system is shown from a density functional theory study to be essential for efficient C-H cleavage, which is a key step in C-H oxidation. Since oxyl species have elongated Mn-O bonds relative to the more usual oxo species of type MnO, the normal expectation would be that high trans-influence ligands X should facilitate oxyl character by elongating the Mn-O bond and thus enhance both oxyl character and reactivity. Contrary to this expectation, but in line with the experimental data (Jin, N.; Ibrahim, M.; Spiro, T. G.; Groves, J. T. J. Am. Chem. Soc. 2007, 129, 12416), we find that reactivity increases along the series X = O(2-) < OH(-) < H2O for the following reasons. The ground-state singlet (S) is unreactive for all X, and only the higher-energy triplet (T) and quintet (Q) states have the oxyl character needed for reactivity, but the higher trans-influence X ligands are also shown to increase the S/T and S/Q gaps, thus making attainment of the needed T and Q states harder. The latter effect is dominant, and high trans-influence X ligands thus disfavor reaction. The higher reactivity in the presence of acid noted by Groves and co-workers is thus rationalized by the preference for having X = H2O over OH(-) or O(2-).
authors.affiliation: Institut Charles Gerhardt Montpellier, UMR 5253 CNRS-UM2-ENSCM-UM1, Universite Montpellier 2, cc-1501 Place Eugene Bataillon, 34095, Montpellier, France.
authors.forename: David
authors.initials: D
authors.lastname: Balcells
authors.forename: Christophe
authors.initials: C
authors.lastname: Raynaud
authors.forename: Robert H
authors.initials: RH
authors.lastname: Crabtree
authors.forename: Odile
authors.initials: O
authors.lastname: Eisenstein
mesh_terms: D006878:Hydroxides / Q000737:chemistry; D008024:Ligands; D017895:Manganese Compounds / Q000737:chemistry*; D008665:Metalloporphyrins / Q000737:chemistry*; D008958:Models, Molecular; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D006878:Hydroxides; D008024:Ligands; D017895:Manganese Compounds; D008665:Metalloporphyrins; D010087:Oxides; D014867:Water; C027424:manganese oxide; C031356:hydroxide ion; D010100:Oxygen