Furan-formic acid dimers: an ab initio and matrix isolation study.

The dimers formed by formic acid (FA) and furan are investigated by ab initio methods and matrix isolation spectroscopy. Nine complexes with binding energies between -3.91 and -0.82 kcal/mol (MP2/6-311++G(d,p) + ZPE + BSSE) are identified. Another five weaker bound complexes are localized at lower level of theory only. The binding in the furan-FA dimers can be described in terms of OH...O, C=O...H, HO...H, CH...O, OH...pi, and CH...pi interactions. Therefore, the furan-FA complexes are classified in two types: (1) the dimers where the OH hydrogen of formic acid interacts with the furan molecule and (2) the dimers where the main interactions of FA with the furan molecule are via the less acidic CH hydrogen. Duning's and Pople's triple and double basis sets were used to study the dependence of the geometries and energies of the complexes from the basis set. BSSE (basis set superposition error) counterpoise corrections (CP) were included during the geometry optimizations of all dimers at the MP2/6-31G(d,p) level of theory. Matrix isolation spectroscopy allowed us to record the IR spectrum of aggregates between FA and furan. By comparison of the experimental IR spectrum with calculated IR spectra of a variety of complexes, it was possible to identify the most stable furan-FA dimer as the major product of the aggregation.

Variation of oxo-transfer reactivity of (nitro)cobalt picket fence porphyrin with oxygen-donating ligands.

Derivatives of (nitro)cobalt picket fence porphyrin with oxygen-donating ligands have been prepared in solution and in the solid state. Crystal structures of two of these derivatives, (H2O)CoTpivPP(NO2) and (CH3OH)CoTpivPP(NO2), have been determined. The ethanol complex (C2H5OH)Co(TPP)(NO2) has been obtained and spectrally characterized using sublimed layers methodology. The formation constant and the DeltaH degrees value of the association reaction with ethanol have been determined by FTIR measurements in CCl4 solution. Catalytic oxygen activation and oxo-transfer reactions of these derivatives have been assessed in solution. Correlations between the oxo-transfer reactivity, thermodynamics, and characteristics of the nitro ligand show that although calculated and observed ONO vibrational spectra and bond lengths suggest activation of the NO2 ligand and enhanced oxo-transfer reactions as seen in the analogous five-coordinate complexes, density functional theory calculations support that thermodynamics limits oxo-atom transfer reactions in these six-coordinate systems.

Interaction of nitrogen oxides with sublimed layers of (meso-tetraphenylporphyrinato)cobalt(II); IR evidence of oxo-transfer from (nitro)porphyrinatocobalt(III) to free nitric oxide.

Interaction of a low-pressure NO2 with sublimed layers of (meso-tetraphenylporphyrinato)cobalt(II) (Co(TPP)) leads to formation of 5-coordinate nitro complex Co(III)(TPP)(NO2). Upon exposure of these layers to pyridine vapors, the fast reaction with formation of 6-coordinate nitro-pyridine porphyrins (Py)Co(III)(TPP)(NO2) occurs. By means of IR spectroscopy and use of nitrogen oxide isotopomers, it is shown that an oxo-transfer reaction occurs from 5-coordinate species to free nitric oxide (NO) while the 6-coordinate complex is rather inert. It is also demonstrated that the stepwise addition of low-pressure NO2 to nitrosyl complex Co(TPP)(NO) leads to formation of the nitro complex most likely by an exchange reaction.