Journal of the American Chemical Society
Article
the experiment, a spectrum at room temperature was recorded to
verify the reversibility of the temperature-dependent process. Line
shape fitting was performed using the WinDNMR software package.53
All chemical shifts, coupling constants, and line width values were set
on the basis of values derived from the experimental spectra. The
exchange rate variable was adjusted to fit the overlaid experimental
spectrum at each temperature.
5.3. Computational Methods. Geometries were optimized in
Gaussian 0954 using the B3LYP55 density functional with the 6-
311+G(d,p) basis set. Geometry optimizations were performed in the
gas phase without symmetry constraint. Stationary points were
characterized by frequency calculations to confirm their identity as
either local minima (zero imaginary frequencies) or first-order saddle
points (one imaginary frequency). For transition structure 2TS, an
intrinsic reaction coordinate (IRC) calculation was conducted to
ensure connection along the potential energy surface to 2. See the
Suporting Information for full details.
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ASSOCIATED CONTENT
■
(18) Bouhadir, G.; Bourissou, D. Chem. Soc. Rev. 2004, 33, 210.
S
* Supporting Information
(19) Mitzel, N. W.; Smart, B. A.; Dreihaupl, K.-H.; Rankin, D. W. H.;
̈
1
Full experimental procedures, H, 13C, and 31P NMR spectra
Schmidbaur, H. J. Am. Chem. Soc. 1996, 118, 12673.
(20) Cowley, A. H.; Dewar, M. J. S.; Goodman, D. W.; Schweiger, J.
R. J. Am. Chem. Soc. 1973, 95, 6506.
for all synthetic compounds, 1H VT-NMR spectra of 4
including spectral simulations, crystallographic details, compu-
tational methods, Cartesian coordinates, and X-ray crystallo-
graphic data in CIF format. This material is available free of
(21) Harvey, R. G.; Schneider, J. F. Hexamethylphosphorous
Triamide. Encyclopedia of Reagents for Organic Synthesis; John Wiley
& Sons, Ltd.: New York, 2001.
(22) Ren, P.; Vechorkin, O.; Allmen, K.; von Scopelliti, R.; Hu, X. J.
Am. Chem. Soc. 2011, 133, 7084.
AUTHOR INFORMATION
Corresponding Author
Notes
■
(23) Nguyen, A. I.; Blackmore, K. J.; Carter, S. M.; Zarkesh, R. A.;
Heyduk, A. F. J. Am. Chem. Soc. 2009, 131, 3307.
(24) NBO 6.0: Glendening, E. D., Badenhoop, J. K., Reed, A. E.,
Carpenter, J. E., Bohmann, J. A., Morales, C. M., Landis, C. R., and
Weinhold, F., Theoretical Chemistry Institute, University of
Wisconsin, Madison, WI, 2013.
The authors declare no competing financial interest.
(25) Prepared by treatment of 2 with elemental selenium. See the
Supporting Information for full experimental and characterization
details.
ACKNOWLEDGMENTS
■
The synthesis and characterization of tricoordinate phosphorus
compounds were supported by the National Science
Foundation under Award CHE-1352164. Additional financial
support was provided by The Pennsylvania State University.
A.T.R. gratefully acknowledges early career support from the
Alfred P. Sloan Foundation. We thank Dr. Sunewang Rixin
Wang for preliminary synthetic work.
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