We report a detailed dynamics and kinetics study of the title reaction over the range of translational energies 0.418 e E tr /kJ mol -1 e 62.760 by employing the quasiclassical trajectory method and a recently reported double many-body expansion potential energy surface for ground-state HO 3 . A comparison of the calculated thermal rate constants with the available experimental results is also presented.

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Quantum chemical calculations at semiempirical (MNDO methods) and ab initio (6-31G and STO-3G basis ses) levels have been performed on boron(III) subphthalocyanines 1-10. Theoretical calculations predict a cone-shaped structure for these compounds independently of the kind of peripheral substitution and even of compositional changes in the central region of the macrocycle (for example, substitution of the boron atom by two hydrogens). The theoretical calculations are in excellent agreement with previous X-ray determinations.

Theoretical calculations were performed for studying the electronic molecular structure of axial subphthalocyanine (SubPc) derivatives. The intermolecular SubPc interactions were also investigated at theoretical level using adequate models. These models represent the interaction of one Cl(OR)-SubPc with the surrounding molecules through the Cl atom as well as the interaction of the Cl-SubPc with an incoming diiminoisoindole group in the first steps of the open ring reaction. The SubPc complexes with more electronegative atoms than Cl heteroatoms in apical positions are more pyramidal than Cl-SubPc. The B-X and B-Np are the most sensitive macrocycle positions with respect to the axial substitutions in SubPcs. The B-X bond has an elevated polarity and seems to correlate with the chemical reactivity of these compounds. The theoretical calculations of the near-frontier orbitals reveal an outstanding energetic and structural homogeneity along the studied series which is in correspondence with the fact that the axial ligand has only a small influence on the position of the maximum bands in UV-vis spectra as well as in the first half-wave potentials for oxidative processes. The study of the intermolecular interactions give information about their influence on the molecular structure of the axial complexes of the SubPcs. The characterization of the interaction of one Cl-SubPc with a pyrrol containing group may be useful in the understanding of the mechanism of the ring expansion reactions. In general, the present results indicate that the apical position may be a critical reactive center both for redox and axial substitution processes.

ABSTRACT:A theoretical investigation on the redox processes in the subphthalocyanines (SubPcs) was performed. Singly and doubly oxidative and reductive transformations were considered. The full geometry optimization of the participating molecules showed that the cone shape arrangement of the SubPc is preserved in their ionic derivatives even when two electrons are either donated or subtracted from the molecule. The biggest geometric changes under electron exchange processes were calculated for the BOCl bond distance. The electronic density distribution over all the products remains almost invariable with respect to the neutral molecule. Our calculations on the neutral and charged SubPcs demonstrated that they behave as conjugated systems, their electronic parameters being correlatively altered by the redox electron exchange. Further, the electronic state of the macrocycle atoms also depends on an intense electronic flow among the macrocyclic skeleton and the surrounding (axial chlorine and peripheral hydrogen) atoms that is associated with the redox process.