Snapshots of an alkylidyne for nitride triple-bond metathesis

Brad C. Bailey, Alison R. Fout, Hongjun Fan, John Tomaszewski, John C. Huffman, J. Brannon Gary, Marc J.A. Johnson, Daniel J. Mindiola

Research output: Contribution to journalArticle

Abstract

The transient titanium alkylidyne complex (PNP)Ti≡ CtBu (PNP = N[2-P(CHMe2)2-4-methylphenyl]2-), [2+2] cycloadds sterically bulky nitriles such as NCR to afford unique examples of kinetically stable azametallacyclobutadienes, (PNP)Ti(NCRCtBu) (R = tBu, 1; Ad, 2). Complexes 1 and 2 can further react with electrophiles such as ClSi(CH3)3 or Al(CH3)3 to extrude the alkyne RC≡ CtBu (R = tBu, 1; R = Ad, 2) and form neutral or zwitterionic titanium imide species, respectively. Imide formation for the latter species results from complete tBuC3- for N3- metathetical exchange. Isotopic labeling studies applying 15N enriched nitrile N≡CAd clearly reveal the nitrogen atom transfer results from incomplete and complete metathesis of a titanium alkylidyne with a nitrile.

Original languageEnglish (US)
Pages (from-to)2234-2235
Number of pages2
JournalJournal of the American Chemical Society
Volume129
Issue number8
DOIs
StatePublished - Feb 28 2007
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Bailey, B. C., Fout, A. R., Fan, H., Tomaszewski, J., Huffman, J. C., Gary, J. B., Johnson, M. J. A., & Mindiola, D. J. (2007). Snapshots of an alkylidyne for nitride triple-bond metathesis. Journal of the American Chemical Society, 129(8), 2234-2235. https://doi.org/10.1021/ja0689684