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due to severely disordered solvent molecules was removed by the use of
the utility SQUEEZE in the PLATON software package.12
Notes and references
‡ General. 1H NMR spectra were recorded on a Varian INOVA-500
(500 MHz) spectrometer, and chemical shifts were reported as the d
scale in ppm relative to CHCl3 as an internal reference for 1H NMR
(d = 7.260 ppm). UV/vis absorption spectra were recorded on a Shimadzu
UV-2550 spectrometer. Mass spectra were recorded on a Bruker microTOF
using the positive mode ESI-TOF method for acetonitrile solutions. Unless
otherwise noted, materials obtained from commercial suppliers were used
without further purification.
1 (a) M. Albrecht and G. van Koten, Angew. Chem., Int. Ed., 2001, 40,
3750; (b) J. Dupont, C. S. Consorti and J. Spencer, Chem. Rev., 2005,
105, 2527; (c) M. E. van der Boom and D. Milstein, Chem. Rev., 2003,
103, 1759; (d) J. T. Singleton, Tetrahedron, 2003, 59, 1837.
2 C. J. Moulton and B. L. Shaw, J. Chem. Soc., Dalton Trans., 1976,
1020.
3 (a) D. P. Arnold, Y. Sakata, K. Sugiura and E. I. Worthington,
Chem. Commun., 1998, 2331; (b) R. D. Hartnell and D. P. Arnold,
Organometallics, 2004, 23, 391; (c) R. D. Hartnell and D. P. Arnold,
Eur. J. Inorg. Chem., 2004, 1262; (d) M. J. Hodgson, P. C. Healy, M. L.
Williams and D. P. Arnold, J. Chem. Soc., Dalton Trans., 2002, 4497;
(e) D. P. Arnold, P. C. Healy, M. J. Hodgson and M. L. Williams,
J. Organomet. Chem., 2000, 607, 41; (f) F. Atefi and D. P. Arnold,
J. Porphyrins Phthalocyanines, 2008, 12, 801; (g) I. K. Morris, K. M.
Snow, N. W. Smith and K. M. Smith, J. Org. Chem., 1990, 55, 1231;
(h) K. Sugiura, A. Kato, K. Iwasaki, H. Miyasaka, M. Yamashita, S.
Hino and D. P. Arnold, Chem. Commun., 2007, 2046.
4 (a) S. Yamaguchi, T. Katoh, H. Shinokubo and A. Osuka, J. Am. Chem.
Soc., 2007, 129, 6392; (b) K. Yoshida, S. Yamaguchi, A. Osuka and H.
Shinokubo, Organometallics, 2010, 29, 3997.
5 (a) S. Yamaguchi, T. Katoh, H. Shinokubo and A. Osuka, J. Am. Chem.
Soc., 2008, 130, 14440; (b) S. Yamaguchi, H. Shinokubo and A. Osuka,
Inorg. Chem., 2009, 48, 795; (c) Y. Matano, K. Matsumoto, Y. Nakano,
H. Uno, S. Sakaki and H. Imahori, J. Am. Chem. Soc., 2008, 130, 4588;
(d) S. Yamaguchi, H. Shinokubo and A. Osuka, J. Am. Chem. Soc.,
2010, 132, 9992.
6 For pincer complexes bearing porphyrins without direct metal–
porphyrin linkages, see: (a) W. T. S. Huck, A. Rohrer, A. T. Anikumar,
R. H. Fokkens, N. M. M. Nibbering, F. C. J. M. van Veggel and D.
N. Reinhoudt, New J. Chem., 1998, 22, 165; (b) I. M. Dixon and J.
P. Collin, J. Porphyrins Phthalocyanines, 2001, 5, 600; (c) B. M. J. M.
Suijkerbuijk, M. Lutz, A. L. Spek, G. van Koten and Klein R. J. M.
Gebbink, Org. Lett., 2004, 6, 3023; (d) B. M. J. M. Suijkerbuijk, D. M.
Tooke, M. Lutz, A. L. Spek, L. W. Jenneskens, G. van Koten and R. J.
M. Klein Gebbink, J. Org. Chem., 2010, 75, 1534.
Compound 2. A toluene/DMF solution (1.5 mL/1.5 mL) of 1 (21.7 mg,
20 mmol) and IrCl3·xH2O (17.7 mg, 50 mmol) were stirred at 100 ◦C for 1 h,
and then the solvent was removed in vacuo. Separation by silica gel column
chromatography (AcOEt/hexane as an eluent) and recrystallization with
CH2Cl2/CH3CN afforded 2 as a green solid (9.0 mg, 6.6 mmol, 33% yield).
1H NMR (CDCl3): d 9.28 (d, J = 5.8 Hz, 2H, pyridyl), 9.00 (s, 2H, b),
8.49 (d, J = 5 Hz, 2H, b), 8.41 (d, J = 5 Hz, 2H, b), 8.09 (d, J = 7.7 Hz,
2H, pyridyl), 7.92 (d, J = 1.6 Hz, 4H, Ar), 7.82 (d, J = 1.9 Hz, 2H, Ar),
7.76 (t, J = 7.7 Hz, 2H, pyridyl), 7.72 (d, J = 1.6 Hz, 2H, Ar), 7.65 (t, J =
1.9 Hz, 1H, Ar), 7.06 (t, J = 6.6 Hz, 2H, pyridyl), 1.51 (s, 36H, tert-butyl),
1.46 (s, 18H, tert-butyl) ppm; UV-vis (CH2Cl2): lmax (e [M-1 cm-1]) = 333
(34000), 369 (32000), 412 (45000), 479 (94000), 576 (15000), 624 (9000)
nm; HR-MS (ESI-MS); m/z = 1346.4564, calc. for [C72H77N6NiIrCl2]+
=
1346.4548 [M - H2O]+. Crystal data for 2: C149.5H174Cl5Ir2N12Ni2O4.5, Mw
=
¯
2890.08, triclinic, space group P1(no. 2), a = 18.4273(18),◦b = 21.224(2), c =
˚
22.036(2) A, a = 73.917(2), b = 67.416(2), g = 64.419(2) , V = 7113.1(12)
3
-3
˚
A , Z = 2, Dc = 1.349 g cm , T = 153(2) K, R = 0.0462 (I > 2.0s(I)), Rw
0.1409 (all data), GOF = 1.019 (I > 2.0s(I)).‡
=
Hydrosilylation with 2. A Schlenk flask charged with iridium porphyrin
pincer complex 2 (5.7 mg, 4.2 mmol) was evacuated and refilled with
nitrogen. To the flask were added ethyl cinnamate (35.0 mL, 0.21 mmol),
toluene (2 mL) and diethoxymethylsilane (50.5 mL, 0.315 mmol). The
mixture was stirred at 50 ◦C for 6 h under a nitrogen atmosphere. The
reaction was quenched with 1 M aq. HCl. The mixture was extracted with
CH2Cl2, and the organic layer washed with water and dried with Na2SO4.
The solvent was removed in vacuo. Purification of the crude product by
silica gel column chromatography (AcOEt/hexane as an eluent) provided
ethyl dihydrocinnamate (35.2 mg, 0.20 mmol) in 94% yield.
7 H. Nishiyama and J. Ito, Chem. Commun., 2010, 46, 203.
8 J. Ito, T. Shiomi and H. Nishiyama, Adv. Synth. Catal., 2006, 348, 1235.
9 The same oxidative conversion of the COD ligand on iridium has been
reported: (a) V. W. Day, T. A. Eberspacher, W. G. Klemperer and B.
Zhong, J. Am. Chem. Soc., 1994, 116, 3119; (b) V. W. Day, W. G.
Klemperer, S. P. Lockledge and D. J. Main, J. Am. Chem. Soc., 1990,
112, 2031; (c) B. de Bruin, P. H. M. Budzelaar and A. W. Gal, Angew.
Chem., Int. Ed., 2004, 43, 4142.
Compound 3. A toluene/DMF solution (1.5 mL/1.5 mL) of 1 (32.6 mg,
30 mmol) and [IrCl(cod)]2 (50.6 mg, 75 mmol) were stirred at 100 ◦C for 1 h,
and then the solvent was removed in vacuo. Separation by silica gel column
chromatography (CH2Cl2/hexane as an eluent) and recrystallization with
CH2Cl2/CH3CN afforded 3 as a green solid (9.4 mg, 7.2 mmol, 24% yield).
1H NMR (CDCl3): d 9.77 (d, J = 4.8 Hz, 1H, pyridyl), 9.09 (s, 1H, b), 9.06
(s, 1H, b), 8.98 (d, J = 4.8 Hz, 1H, Py), 8.61 (d, J = 7.8 Hz, 1H, Py), 8.50
(d, J = 5.0 Hz, 1H, b), 8.49 (d, J = 5.0 Hz, 1H, b), 8.46 (d, J = 5.0 Hz, 1H,
b), 8.45 (d, J = 5.0 Hz, 1H, b), 8.33 (d, J = 7.9 Hz, 1H, pyridyl), 7.91 (t, J =
7.1 Hz, 1H, pyridyl), 7.83 (t, J = 7.8 Hz, 1H, pyridyl), 7.69 (m, 2H, Ar-para),
7.63 (m, 1H, Ar-para), 7.22 (m, 2H, pyridyl), 4.43 (m, 1H, C8H10O ligand),
3.80 (t, J = 7.9 Hz, 1H, C8H10O ligand), 2.99 (dd, J = 3.6, 15 Hz, 1H,
C8H10O ligand), 2.63 (m, 1H, C8H10O ligand), 2.44 (dd, J = 9.3, 13.5 Hz,
1H, C8H10O ligand), 1.7–1.2 (55H, tert-butyl + C8H10O ligand), 0.75 (m,
1H, C8H10O ligand), 0.63 (m, 1H, C8H10O ligand), 0.29 (dd, J = 4.5, 11 Hz,
1H, C8H10O ligand), -0.83 (m, 1H, C8H10O ligand) ppm. Signals of the
ortho-protons of the 3,5-di-tert-butylphenyl groups could not be clearly
assigned due to broadening; UV-vis (CH2Cl2): lmax (e [M-1 cm-1]) = 334
(29000), 377 (22000), 430 (43000), 489 (70000), 597 (9000), 649 (14000)
10 S. T. Madrahimov, D. Markovic and J. F. Hartwig, J. Am. Chem. Soc.,
2009, 131, 7228.
11 (a) J.-P. Sutter, S. L. James, J. P. Steenwinkel, T. Karlen, D. M. Grove,
G. N. Veldman, W. J. J. Smeets, A. L. Spek and G. van Koten,
Organometallics, 1996, 15, 941; (b) H. C. L. Abbenhuis, N. Feiken,
D. M. Grove, J. T. B. H. Jastrzebski, H. Kooijman, P. von der Sluis, W.
J. J. Smeets, A. L. Spek and G. van Koten, J. Am. Chem. Soc., 1992,
114, 9773; (c) M. P. Hogerheide, D. M. Grove, J. Boersma, J. T. B.
H. Jastrzebski, H. Kooijman, A. L. Spek and G. van Koten, Chem.–
Eur. J., 1995, 1, 343; (d) F. Carre, C. Chuit, R. J. P. Corriu, A. Mehdi
and C. Reye, Organometallics, 1995, 14, 2754; (e) M. P. Hogerheide,
J. Boersma, A. L. Spek and G. van Koten, Organometallics, 1996, 15,
1505.
nm; HR-MS (ESI-MS): m/z = 1398.5937, calc. for [C80H87OIrN6Ni]+
=
1398.5915 [M]+. Crystal data for 3: C188H216Ir2N26Ni2O2, Mw = 3373.69,
¯
12 (a) SQUEEZE-PLATON: A. L. Spek, PLATON, A Multipurpose
Crystallographic Tool, Utrecht University, Utrecht, The Netherlands,
2005; (b) P. van der Sluis and A. L. Spek, Acta Crystallogr., Sect. A:
Found. Crystallogr., 1990, 46, 194.
triclinic, space group P1(no. 2), a = 13.195(5), b = 17.790(5), c = 35.311(5)
◦
3
˚
˚
A, a = 86.438(5), b = 84.753(5), g = 81.444(5) , V = 8152(4) A , Z = 2,
Dc = 1.374 g cm-3, T = 153(2) K, R = 0.0849 (I > 2.0s(I)), Rw = 0.2166
(all data), GOF = 1.093 (I > 2.0s(I)).‡ Some unassigned electron density
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 8773–8775 | 8775
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