Flores, Jaime A. and Cavaliere, Vincent N. and Buck, Dominik and Pintér, Balázs and Chen, George and Crestani, Marco G. and Baik, Mu-Hyun and Mindiola, Daniel J. (2011) Methane activation and exchange by titanium-carbon multiple bonds. Chemical Science, 2 (8). pp. 1457-1462. ISSN 2041-6520 http://resolver.caltech.edu/CaltechAUTHORS:20110805-095203741
- Published Version
See Usage Policy.
PDF (Supplementary Information)
- Supplemental Material
See Usage Policy.
Use this Persistent URL to link to this item: http://resolver.caltech.edu/CaltechAUTHORS:20110805-095203741
We demonstrate that a titanium-carbon multiple bond, specifically an alkylidyne ligand in the transient complex, (PNP)Ti≡C^(t)Bu (A) (PNP^− = N[2-P(CHMe_2)_(2)-4-methylphenyl]_2), can cleanly activate methane at room temperature with moderately elevated pressures to form (PNP)Ti=CHtBu(CH_3). Isotopic labeling and theoretical studies suggest that the alkylidene and methyl hydrogens exchange, either via tautomerization invoking a methylidene complex, (PNP)Ti=CH_(2)(CH_(2)^(t)Bu), or by forming the methane adduct (PNP)Ti≡C^(t)Bu(CH_4). The thermal, fluxional and chemical behavior of (PNP)Ti=CH^(t)Bu(CH_3) is also presented in this study.
|Additional Information:||© 2011 Royal Society of Chemistry. Received 09 Mar 2011, Accepted 28 Apr 2011; First published on the web 02 Jun 2011. Financial support of this research was provided by the National Science Foundation (CHE-0848248, CHE-0645381). D.J.M. acknowledges support from the Alexander von Humboldt Stiftung for a Friedrich Bessel Research Award and M.H.B. thanks the Research Corporation for funding. D.B. and D.J.M. thank Prof. John E. Bercaw and Dr Edward Weintrob for insightful discussions and for allowing usage of their high-pressure setup. Dr Jonathan A. Karty is also thanked for assistance with analytical methods. M.G.C. thanks CONACYT for a postdoctoral fellowship.|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Jason Perez|
|Deposited On:||05 Aug 2011 22:59|
|Last Modified:||26 Dec 2012 13:27|
Repository Staff Only: item control page