FULL PAPER
Ar), 7.35 (m, 4 H, Ar), 7.12 (m, 6 H, Ar), 7.03 (m, 8 H, Ar), 6.87
tron density at the BCPs. The analysis was done with the AIMALL
(m, 4 H, Ar), 6.77 (m, 2 H, Ar) ppm. 31P NMR (CD2Cl2, 400 MHz, program[27] by using the wavefunctions obtained from the DFT cal-
223 K): δ = –16.9 (s) ppm. 13C NMR (CD2Cl2, 400 MHz, 223 K): culations with the computationally optimized structures.
δ = 212.9 (s, COS), 154.7 (m, C metalated), 145.4–124.0 (Ar) ppm.
Acetoxylation of 2-Phenylpyridine: 2-Phenylpyridine (60 μL,
0.33 mmol), PhI(OAc)2 (326 mg, 1 mmol), and catalyst (2a or 2b,
Acknowledgments
0.015 mmol) were mixed in solvent (2.2 mL), and the solution was
The authors are grateful to Servei Central de Suport a la In-
heated at the indicated temperature and time. The solvent was re-
vestigació Experimental (SCSIE) of the Universitat de València for
moved under vacuum, and the resulting solid was purified by silica
instrumental support. Financial support provided by the Inorganic
gel column chromatography with hexanes/ethyl acetate (90:10) as
Materials Chemistry Graduate Program (EMTKO) and the strate-
gic funding of the University of Eastern Finland is gratefully ac-
knowledged (grant to A. O.). The computational work has been
facilitated by the use of the Finnish Grid Infrastructure resources.
the eluent.
1
Compound 5: H NMR (CDCl3, 400 MHz, 298 K): δ = 8.77 (ddd,
JH,H = 6.0, JH,H = 1.8, JH,H = 1.0 Hz, 1 H), 7.85 (m, 1 H), 7.71
(dd, JH,H = 7.6, JH,H = 2.0 Hz, 1 H), 7.59 (m, 1 H), 7.46 (m, 1 H),
7.38 (dd, JH,H = 7.6, JH,H = 1.3 Hz, 1 H), 7.34 (m, 1 H), 7.20 (dd,
JH,H = 8.0, JH,H = 1.3 Hz, 1 H), 2.18 (s, 3 H, CH3) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 169.3 (s, Cquat.), 154.9 (s, Cquat.), 148.6 (s,
[1] a) D. C. Powers, T. Ritter, Top. Organomet. Chem. 2011, 35,
129–156; b) L. M. Mirica, J. R. Khusnutdinova, Coord. Chem.
Rev. 2013, 257, 299–314.
CH), 148.0 (s, Cquat.), 137.5 (s, CH), 131.8 (s, Cquat.), 130.9 (s, CH), [2] F. A. Cotton, J. Gu, C. A. Murillo, D. J. Timmons, J. Am.
Chem. Soc. 1998, 120, 13280–13281.
130.2 (s, CH), 126.5 (s, CH), 124.2 (s, CH), 123.2 (s, CH), 122.6 (s,
CH), 20.9 (s, CH3) ppm.
[3] a) F. A. Cotton, I. O. Koshevoy, P. Lahuerta, C. A. Murillo, M.
Sanaú, M. A. Úbeda, Q. Zhao, J. Am. Chem. Soc. 2006, 128,
13674–13679; b) D. Penno, V. Lillo, I. O. Koshevoy, M. Sanaú,
M. A. Úbeda, P. Lahuerta, E. Fernández, Chem. Eur. J. 2008,
14, 10648–10655; c) D. Penno, E. Estevan, F. Fernández, P.
Hirva, P. Lahuerta, M. Sanaú, M. A. Úbeda, Organometallics
2011, 30, 2083–2094; d) S. Ibañez, F. Estevan, P. Hirva, M.
Sanaú, M. A. Úbeda, Organometallics 2012, 31, 8098–8108; e)
S. Ibañez, D. N. Vrecˇko, F. Estevan, P. Hirva, M. Sanaú, M. A.
Úbeda, Dalton Trans. 2014, 43, 2961–2970; f) S. Ibañez, L.
Oresmaa, F. Estevan, P. Hirva, M. Sanaú, M. A. Úbeda, Orga-
nometallics 2014, 33, 5378–5391.
Direct Catalytic Phenylation of 1-Methylindole and Indole: The pro-
cedure reported by Sanford and co-workers was followed.[10] 1-
Methylindole (6a) or indole (6b; 58.6 mg, 0.5 mmol), and the pre-
catalyst 2a or 2b (0.0125 mmol, 2.5 mol-% of Pd) were dissolved in
CH3CO2H (5 mL), and the solution was stirred at 298 K for 5 min.
[Ph2I]PF6 (426.0 mg, 1 mmol) was added, and the resulting solution
was stirred at 298 K. The reaction mixture was filtered through a
plug of siliceous earth, and the solvents were evaporated to dryness.
The resulting oil was dissolved in CH2Cl2 (25 mL) and extracted
with aqueous NaHCO3 (2ϫ 40 mL). The organic phase was dried
with Na2SO4 and concentrated, and the product was purified by
silica gel chromatography with hexanes/ethyl acetate (96:4) as the
eluent.
[4] a) D. C. Powers, T. Ritter, Nature 2009, 1, 302–309; b) D. C.
Powers, M. A. L. Geibel, J. E. M. N. Kein, T. Ritter, J. Am.
Chem. Soc. 2009, 131, 17050–17051; c) G. J. Chuang, W. Wang,
E. Lee, T. Ritter, J. Am. Chem. Soc. 2011, 133, 1760–1762.
[5] M. G. Campbell, D. C. Powers, J. Raynaus, M. J. Graham, P.
Xie, E. Lee, T. Ritter, Nature Chem. 2011, 3, 949–953.
[6] D. C. Powers, T. Ritter, Organometallics 2013, 32, 2042–2045.
[7] a) J. R. Khusnutdinova, N. P. Rath, L. M. Mirica, Angew.
Chem. Int. Ed. 2011, 50, 5532–5536; b) S. E. Eitel, M. Bauer,
D. Schweinfurth, N. Deibel, B. Sarkar, H. Kelm, H.-J. Krüger,
W. Frey, R. Peters, J. Am. Chem. Soc. 2012, 134, 4683–4693.
[8] a) A. J. Canty, A. Ariafard, M. S. Sanford, B. F. Yates, Organo-
metallics 2013, 32, 544–555; b) J. Le Bras, J. Muzard, Chem.
Rev. 2011, 111, 1170–1214; c) T. Yoneyama, R. H. Crabtree, J.
Mol. Catal. A 1996, 108, 35–40; d) L. M. Stock, K.-t. Tse, L. J.
Vorvick, S. A. Walstrum, J. Org. Chem. 1981, 46, 1757–1759.
[9] N. R. Deprez, M. S. Sanford, Inorg. Chem. 2007, 46, 1924–
1935.
[10] A. J. Hickman, M. S. Sanford, Nature 2012, 484, 177–185.
[11] a) D. C. Powers, D. Benitez, E. Tkatchouk, W. A. Goddard, T.
Ritter, J. Am. Chem. Soc. 2010, 132, 14092–14103; b) D. C.
Powers, D. Y. Xiao, M. A. L. Geibel, T. Ritter, J. Am. Chem.
Soc. 2010, 132, 14530–14536; c) D. C. Powers, T. Ritter, Acc.
Chem. Res. 2012, 45, 840–850.
[12] J. R. Khusnutdinova, N. P. Rath, L. M. Mirica, Angew. Chem.
Int. Ed. 2011, 50, 5532–5536.
[13] S. R. Neufeld, M. S. Sanford, Acc. Chem. Res. 2012, 45, 936–
946.
1
3
Compound 8a: H NMR (CDCl3, 400 MHz): δ = 7.75 (d, JH,H
=
3
7.6 Hz, 1 H), 7.63–7.60 (m, 2 H), 7.56 (t, JH,H = 7.6 Hz, 2 H),
3
3
7.51–7.45 (m, 2 H), 7.36 (dt, JH,H = 8.0, JH,H = 1.2 Hz, 1 H),
7.26 (m, 1 H), 6.68 (s, 1 H), 3.83 (s, 3 H, CH3) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 141.7 (s, Cquat.), 138.5 (s, Cquat.), 132.9 (s,
Cquat.), 129.5 (s, 2 CH), 128.6 (s, 2 CH), 128.1 (s, Cquat.), 127.9 (s,
CH), 121.8 (s, CH), 120.6 (s, CH), 120.0 (s, CH), 109.7 (s, CH),
101.8 (s, CH), 31.2 (s, CH3) ppm.
1
Compound 8b: H NMR (CDCl3, 400 MHz): δ = 8.31 (br s, 1 H),
3
7.69–7.65 (m, 3 H), 7.49–7.39 (m, 3 H), 7.356 (t, JH,H = 7.4 Hz, 1
3
3
3
H), 7.23 (ddd, JH,H = 7.8, JH,H = 7.0, JH,H = 1.2 Hz, 1 H), 7.16
3
3
3
(ddd, JH,H = 7.7, JH,H = 7.0, JH,H = 1.0 Hz, 1 H), 6.86 (s, 1 H)
ppm. 13C NMR (CDCl3, 100 MHz): δ = 137.8 (s, Cquat.), 136.7 (s,
Cquat.), 132.2 (s, Cquat.), 129.2 (s, 2 CH), 129.0 (s, 2 CH), 127.7 (s,
Cquat.), 125.1 (s, CH), 122.3 (s, CH), 120.6 (s, CH), 120.2 (s, CH),
110.9 (s CH), 99.9 (s, CH) ppm.
Computational Details: All models were fully optimized with the
Gaussian09 program package[23] at the DFT level of theory. The
hybrid density functional B3PW91[24,25] was utilized together with
a basis set consisting of the Stuttgart–Dresden effective core poten-
tial basis set with an additional p-polarization function for Pd
atoms [SDD(p)] and the standard all-electron basis set 6-31G(d)
[14] A. R. Dick, K. L. Hull, M. S. Sanford, J. Am. Chem. Soc. 2004,
126, 2300–2301.
for all other atoms. Frequency calculations with no scaling were [15] N. R. Deprez, D. Kalyani, A. Krause, M. S. Sanford, J. Am.
Chem. Soc. 2006, 128, 4972–4973.
[16] I. O. Koshevoy, P. Lahuerta, M. Sanaú, M. A. Úbeda, A. Do-
menech, Dalton Trans. 2006, 5536–5541.
[17] a) I. V. Umakoshi, A. Ichimura, I. Kinoshita, S. Ooi, Inorg.
Chem. 1990, 29, 4005–4010; b) A. C. Durrell, M. N. Jackson,
N. Hazari, H. B. Gray, Eur. J. Inorg. Chem. 2013, 1134–1137.
conducted to ensure optimization to true minima. None of the op-
timized structures gave imaginary frequencies.
Topological charge-density analysis was performed by the
QTAIM[26] method, which allowed us to access the nature of the
bonding through the calculation of different properties of the elec-
Eur. J. Inorg. Chem. 2015, 2822–2832
2831
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