H.-C. Böttcher et al. / Inorganic Chemistry Communications 14 (2011) 377–379
379
(FAB+): m/z=538 [M+]. 1H NMR (400 MHz, CDCl3): δ 8.40 (m, 2H, ptpy), 7.86 (m,
4H, ptpy), 7.50 (d, J=7.68 Hz, 2 H, ptpy), 7.18 (m, 2H, ptpy), 6.73 (d, J = 7.68 Hz, 2H,
ptpy), 6.04 (s, 2H, ptpy), 5.29 (s, 1H, CH-acac), 2.02 (s, 6 H, CH3-ptpy), 1.83 (s, 6H,
CH3-acac). 13C {1H} NMR (100 MHz, CDCl3): δ 187.3 (CO-acac), 168.2 (d, JRh-C=35.5
Hz, C metalated), 165.1, 148.9, 141.8, 138.8, 137.1, 134.6, 123.4, 123.1, 121.5, 118.5,
97.9 (CH-acac), 28.7 (ptpy-CH3), 21.5 (CH3-acac).
Acknowledgments
The authors are grateful to the Department of Chemistry of the
Ludwig Maximilians University Munich and to the Fraunhofer Institut
für Angewandte Polymerforschung, Golm/Germany for supporting
these investigations. The Johnson Matthey plc, Reading, UK, we thank
for a generous loan of hydrated RhCl3. Sandra Albrecht we thank for
collecting the X-ray crystal data.
[11] Synthesis of [Rh(ptpy)3] (4): To a solution of 1 (359 mg, 0.50 mmol) in 20 mL of
THF solid Na(acac)⋅H2O (140 mg, 1 mmol) was added and the mixture stirred for
1 h at room temperature. The solvent was removed in vacuo, the remaining
residue dissolved in 5 mL of 2-(p-tolyl)pyridine and the mixture refluxed (268 °C)
for 20 min. The solution was cooled to room temperature and the crude product
precipitated by adding 30 mL of hexane. The slight yellow powder was filtered off
and washed tree times with 10 mL portions of hexane and dried in vacuo. The
product was purified by filtration on alumina with dichloromethane as the eluent.
Yield: 321 mg (53%). Anal. Calc. for C36H30N3Rh: C, 71.17; H, 4.89; N, 6.92. Found:
C, 71.21; H, 4.84; N, 6.79%. 1H NMR (400 MHz, CDCl3): δ 7.86 (d, m, 3H, ptpy), 7.66
(m, 3H, ptpy), 7.58 (d, J=8 Hz, 3H, ptpy), 7.49 (m, 3H, ptpy), 6.88 (m, 3H, ptpy),
6.72 (m, 3H, ptpy), 6.65 (s, 3H, ptpy), 2.00 (s, 9H, CH3). Due to solubility problems
no 13C-NMR spectra could be obtained, that showed all quaternary carbon atoms.
MS (FAB+): m/z=607 [M+].
References
[1] H.-C. Böttcher, M. Graf, K. Sünkel, P. Mayer, H. Krüger, Inorg. Chim. Acta (2010),
[2] M. Graf, V. Gancheva, M. Thesen, H. Krüger, P. Mayer, K. Sünkel, Inorg. Chem. Commun.
11 (2008) 2318 and references cited therein.
[3] S.-K. Leung, K.Y. Kwok, K.Y. Zhang, K.K.-W. Lo, Inorg. Chem. 49 (2010) 49848 and
references cited therein.
[4] T. Matsumoto, R.A. Periana, D.J. Taube, H. Yoshida, J. Catal. 206 (2002) 272.
[5] M.G. Colombo, T.C. Brunold, T. Riedener, H.U. Güdel, M. Förtsch, H.-B. Bürgi, Inorg. Chem.
33 (1994) 545.
[12] A.B. Tamayo, B.D. Alleyne, P.I. Djurovic, S. Lamansky, I. Tsyba, N.N. Ho, R. Bau, M.E.
Thompson, J. Am. Chem. Soc. 125 (2003) 7377.
[13] Single crystals of
3 were obtained by slow diffusion of iso-hexane into a
dichloromethane solution of the compound overnight. A suitable crystal was selected
by means of a polarization microscope, mounted on the tip of a glass fiber, and
investigated on an Oxford XCalibur diffractometer using Mo Kα radiation
(λ=0.71073 Å). The intensities were corrected for absorption by an empirical
correction with SCALE3 ABSPACK [14]. The structure was solved by direct methods
(SIR 97) [15] and refined by full-matrix least-squares calculations on F2 (SHELXL-97)
[16]. Anisotropic displacement parameters were refined for all non-hydrogen atoms.
Crystal data: C30H29Cl2N2O2Rh (3⋅CH2Cl2) FW=623.36, triclinic, space group P-1,
a=8.0821(2), b=12.3285(3), c=13.8138(3)Å, α=85.7270(10)° β=89.6400
(10)° γ=79.2410(10)° V=1348.41(6)Å3, Z=2, Dcalc=1.5535 g cm–3, T=200(2)
K, 13843 reflections were collected, of which 7250 (Rint=0.0392 [IN2σ (I)] were
unique.
[6] (a) S. Sprouse, K.A. King, P.J. Spellane, R.J. Watts, J. Am. Chem. Soc. 106 (1984) 6647;
(b) F.O. Garces, K.A. King, R.J. Watts, Inorg. Chem. 27 (1988) 3464.
[7] J.M. Burke, R.B. Coapes, A.E. Goeta, J.A.K. Howard, T.B. Marder, E.G. Robins, S.A.
Westcott, J. Organomet. Chem. 649 (2002) 199.
[8] H.-C. Böttcher, M. Graf, K. Sünkel, H. Krüger, Inorg. Chim. Acta, submitted.
[9] A. Van der Ent, A.L. Onderdelinden, Inorg. Synth. 28 (1990) 90.
[10] Synthesis of [Rh(acac)(ptpy)2] (3): To a solution of 1 (359 mg, 0.50 mmol) in 20 mL
of THF solid Na(acac)⋅H2O (140 mg, 1 mmol) was added. Immediately a clear deep
orange solution resulted which was stirred for 1 h at room temperature. Then the
solvent was removed in vacuo. The remaining residue was extracted with 30 mL of
hexane and filtered to remove the NaCl. The solution was evaporated to dryness and
the residue was dissolved in 20 mL of toluene. 2-(p-tolyl)pyridine (845 mg, 5 mmol)
was added and the mixture refluxed with stirring for 2 h. After cooling to room
temperature the solvent was evaporated to dryness, the residue was dissolved in a
minimum of dichloromethane, and 3 precipitated by adding 30 mL of hexane. The
yellow crystals were filtered off, washed three times with 10 mL portions of hexane
and dried in vacuo. The crude product was chromatographed on alumina
with dichloromethane as the eluent. Yield: 350 mg (65%). Anal. Calcd. for
[14] SCALE3 ABSPACK: Empirical absorption correction, CRYSALIS – Software Package,
Oxford Diffraction Ltd, 2006.
[15] A. Altomare, M.C. Burla, M. Camalli, G.L. Cascarano, C. Giacovazzo, A. Guagliardi, A.
G.G. Moliterni, G. Polidore, R. Spagna, SIR97: a new tool for crystal structure
determination and refinement, J. Appl. Crystallogr. 32 (1999) 115.
[16] G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112.
C29H27N2O2Rh: C, 64.69; H, 5.05; N, 5.20. Found: C, 64.61; H, 5.07; N, 5.15%. MS