Singlet-triplet splittings and 1,2-hydrogen shift barriers for methylphenylborenide, methylphenylcarbene, and methylphenylnitrenium in the gas phase and solution. What a difference a charge makes

Research output: Contribution to journalArticle

54 Scopus citations

Abstract

In the isoelectronic series methylphenylborenide, methylphenylcarbene, and methylphenylnitrenium, fundamental differences are predicted for singlet state geometries, singlet-triplet state splittings, barriers to singlet 1,2- hydrogen migration, and sensitivity of 1,2-hydrogen migration to solvent effects in n-heptane and acetonitrile. We conclude that isoelectronic analogies are dangerous for systems having different formal charges, and that the interaction of the divalent center with a conjugating substituent is very sensitive to the electron donating or withdrawing nature (and power) of the hypovalent atom. Solvent effects on the singlet-triplet splitting result from static polarity differences whereas the solvent effects on 1,2-hydrogen migration result primarily from polarizability differences. For the experimentally characterized carbene case, extensive comparison of calculated and measured results is provided.

Original languageEnglish (US)
Pages (from-to)12338-12342
Number of pages5
JournalJournal of the American Chemical Society
Volume119
Issue number50
DOIs
StatePublished - Dec 17 1997

Fingerprint Dive into the research topics of 'Singlet-triplet splittings and 1,2-hydrogen shift barriers for methylphenylborenide, methylphenylcarbene, and methylphenylnitrenium in the gas phase and solution. What a difference a charge makes'. Together they form a unique fingerprint.

  • Cite this