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Scheme 3. Possible Mechanism for the Formation of 4 [Ar0 =
2,6-(Me2NCH2)2C6H3]
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A rationale consistent with these data and based on the earlier
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t
(OC6H3 Bu2-2,6)2 (A) is conceivable, given that 6 can be
formed. If this crowded complex A undergoes BiꢀO bond
homolysis as postulated in the literature14 to form a bismuth
t
radical (B) and the OC6H3 Bu2-2,6 radical (C), the latter species
could rearrange to D and then be captured by B.
Following the rearrangement to D, the para CꢀH would now be
adjacent to the aryloxide ligand in E. In the crowded environment
enforced by the tert-butyl substituents, this could eliminate the
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t
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’ ASSOCIATED CONTENT
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S
Supporting Information. Full experimental details; crys-
b
tallographic collection data and selected metrical parameters for
2ꢀ6 (Tables S1ꢀS4 and CIF); ORTEP drawings of the full
asymmetric units for 3, 4, and 6 (Figures S1ꢀS3); computational
details; and calculated IR spectra for 4 and 5 (Figure S4). This
acs.org. CCDC 811909ꢀ811914 contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data
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’ AUTHOR INFORMATION
(31) Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen,
A. G.; Taylor, R. J. Chem. Soc., Perkin Trans. 2 1987, S1.
(32) Morita, Y.; Ueda, A.; Nishida, S.; Fukui, K.; Ise, T.; Shiomi, D.;
Sato, K.; Takui, T.; Nakasuji, K. Angew. Chem., Int. Ed. 2008, 47, 2035.
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Corresponding Author
’ ACKNOWLEDGMENT
(34) Ashkenazi, N.; Vigalok, A.; Parthiban, S.; Ben-David, Y.;
Shimon, L. J. W.; Martin, J. M. L.; Milstein, D. J. Am. Chem. Soc. 2000,
122, 8797.
(35) Yasui, M.; Kikuchi, T.; Iwasaki, F.; Suzuki, H.; Murafuji, T.;
Ogawa, T. J. Chem. Soc., Perkin Trans. 1 1990, 3367.
(36) Staroverov, V. N.; Scuseria, G. E.; Tao, J.; Perdew, J. P. J. Chem.
Phys. 2003, 119, 12129.
We thank the Chemical Sciences, Geosciences, and Bios-
ciences Division of the Office of Basic Energy Sciences of the
Department of Energy and Idaho National Laboratory through
Dr. Bruce Mincher for support. We also thank Ryan A. Zarkesh
for assistance with X-ray crystallography and Dr. N. R. M.
Crawford for help with the computations. This aspect of the
work was supported by the National Science Foundation (Grant
CHE-0840513).
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dx.doi.org/10.1021/ja201128d |J. Am. Chem. Soc. 2011, 133, 5244–5247