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Rearrangements in icosahedral boranes and carboranes revisited.

ABSTRACT: The structure, stability, and intermolecular rearrangements between ortho-, meta-, and para-C2B10H12 and were investigated using the hybrid density functional B3LYP/6-31G(d) for vibrational frequencies, as well as B3LYP/6-311+G(2d,p) for single-point electronic energies. The general trends in free energies of rearrangement between ortho-C2B10H12 to meta-C2B10H12 and meta-C2B10H12 to para-C2B10H12 presented here are consistent with experimental reaction temperatures. In addition, the majority of the rearrangements can be viewed in terms of concerted diamond-square-diamond steps and triangular face rotations.

SUBMITTER: Brown CA

PROVIDER: S-EPMC2441500 | biostudies-literature | 2006 Jul

REPOSITORIES: biostudies-literature

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Rearrangements in icosahedral boranes and carboranes revisited.

Brown Christopher A CA McKee Michael L ML

Journal of molecular modeling 20060701 5

The structure, stability, and intermolecular rearrangements between ortho-, meta-, and para-C2B10H12 and were investigated using the hybrid density functional B3LYP/6-31G(d) for vibrational frequencies, as well as B3LYP/6-311+G(2d,p) for single-point electronic energies. The general trends in free energies of rearrangement between ortho-C2B10H12 to meta-C2B10H12 and meta-C2B10H12 to para-C2B10H12 presented here are consistent with experimental reaction temperatures. In addition, the majority of ...[more]

PMID: 16261296

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Project description:Nitrenium ion species are examined using computational methods (DFT, MP2, coupled-cluster, and a composite method, CBS-APNO) with a particular emphasis on nonaromatic species (i.e., those lacking an aromatic or heteroaromatic ring in direct conjugation with the formal nitrenium ion center.) The substitution of the N+ center with alkyl, alkoxy, vinyl, acyl, and sulfonyl, among others, was evaluated. For these species, three properties are considered. (1) The stability of the nitrenium ions to unimolecular isomerizations such as 1,2 alkyl or H shifts; to the extent that the singlet states could be characterized as discrete minima on the potential energy surface (PES), (2) the effect of the substituents on singlet-triplet energy splitting as well as (3) the relative stabilities of the nitrenium ions as defined by N-hydration enthalpies (RR'N+ + H2O → RR'NOH2 +). Nearly all simple alkyl and di-alkyl nitrenium ion singlet states are predicted to rearrange without detectable barriers, largely through 1,2 H or alkyl shifts. Methyl and N,N-dimethylnitrenium ion singlet states could be characterized as formal minima on the PES. However, these species show small or insignificant barriers to isomerization. Disubstituted nitrenium ions that include an alkyl group and a conjugating substituent such as alkoxyl, vinyl, or phenyl show meaningful barriers to isomerization and are thus predicted to possess nontrivial lifetimes in solution. Alkyl groups substantially stabilize the singlet state relative to the situation in the parent nitrenium ion NH2 + to the point where the two states are nearly degenerate. Other groups that interact with the nitrenium ion center decrease the ΔE st in the order formoyl < vinyl < phenyl < alkoxy ∼ sulfonyl < cyclopropyl ∼ cyclobutyl. The latter two substituents interact strongly with the (singlet) nitrenium ion center through the formation of a nonclassical bonding reminiscent of the bisected cyclopropylcarbinyl ion case for carbocations. When singlet-state stability is evaluated in the context of N-hydration enthalpies, it is found that the ordering is acyl < vinyl < alkoxyl < phenyl < cyclopropyl and cyclobutyl.

Dataset Information

Rearrangements in icosahedral boranes and carboranes revisited.

Publications

Rearrangements in icosahedral boranes and carboranes revisited.

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