A theoretical investigation into dimethylcarbene and its diamino and diphosphino analogs: Effects of cyclization and unsaturation on the stability and multiplicity

M. Z. Kassaee, M. Ghambarian, S. M. Musavi, F. A. Shakib, M. R. Momeni

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

Abstract

High levels of ab initio and DFT calculations (B3LYP/6-311++ G**, B3LYP/AUG-cc-pVTZ, and CCSD(T)/6-311++G** levels) coupled with isodesmic reactions are used to compare and contrast the multiplicities and relative stabilities of singlet (s) and triplet (t) acyclic carbenes, including: dimethylcarbene, diaminocarbene, and diphosphinocarbene along with their saturated and unsaturated cyclic ones. Cyclization is unfavorable for all acyclic carbenes while unsaturation of cyclic analogs appears favorable. The simultaneous cyclization and unsaturation of dimethyl- carbene increases the singlet-triplet energy gap (δ£s-t), while for diphosphinocarbene the situation is reversed. For diaminocarbene the increase of δEs-t is encountered only during cyclization.

Original languageEnglish (US)
Pages (from-to)919-924
Number of pages6
JournalJournal of Physical Organic Chemistry
Volume22
Issue number10
DOIs
StatePublished - Oct 2009

Keywords

  • Ab initio
  • DFT
  • Diaminocarbene
  • Dimethylcarbene
  • Diphosphinocarbene
  • Isodesmic reaction
  • Multiplicity

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