with acetonitrile and later acetonitrile/water/saturated aqueous
KNO3 (50 : 3 : 1). The product eluents were concentrated to
dryness, and the resulting material was dissolved in minimal
amounts of ethanol/water. The product was precipitated by
the addition of excess solid NH4PF6. The orange precipitate
was centrifuged, washed twice with water, and then dried
under high vacuum to afford L-7 (3.3 mg, 30% from 5). The
L-configuration was assigned by CD spectroscopy. An er of
96 : 4 was determined by chiral HPLC analysis under the
following conditions: Daicel Chiralcel OD-R, 250 ꢁ 4 mm,
6 For a review on chiral-auxiliary-mediated asymmetric coordination
chemistry, see: E. Meggers, Chem.–Eur. J., 2010, 16, 752–758.
7 (a) H. B. Jonassen, J. C. Bailar, Jr. and E. H. Huffman, J. Am.
Chem. Soc., 1948, 70, 756–758; (b) C. F. Liu, N. C. Liu and
J. C. Bailar, Jr., Inorg. Chem., 1964, 3, 1085–1087.
8 (a) D. Hesek, Y. Inoue, S. R. L. Everitt, H. Ishida, M. Kunieda
and M. G. B. Drew, Inorg. Chem., 2000, 39, 317–324; (b) D. Hesek,
Y. Inoue, H. Ishida, S. R. L. Everitt and M. G. B. Drew, Tetra-
hedron Lett., 2000, 41, 2617–2620.
9 F. Pezet, J.-C. Daran, I. Sasaki, H. Aıt-Haddou and G. G. A.
¨
Balavoine, Organometallics, 2000, 19, 4008–4015.
10 R. J. Warr, A. C. Willis and S. B. Wild, Inorg. Chem., 2006, 45,
8618–8627.
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Chambron, J.-P. Sauvage and J. Lacour, Angew. Chem., Int. Ed.,
2002, 41, 2317–2319; (b) O. Hamelin, J. Pecaut and M. Fontecave,
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Chem.–Eur. J., 2004, 10, 2548–2554.
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Soc., 2009, 131, 9602–9603.
13 L. Gong, S. P. Mulcahy, D. Devarajan, K. Harms, G. Frenking
and E. Meggers, Inorg. Chem., 2010, 49, 7692–7699.
14 L. Gong, Z. Lin, K. Harms and E. Meggers, Angew. Chem., Int.
Ed., 2010, 49, 7955–7957.
flow rate 0.5 ml minꢀ1
, column temperature 40 1C,
UV-detection at 254 nm, solvent A = 0.087% H3PO4, solvent
B = MeCN, with a linear gradient of 15% to 30% B in 20 min.
1H-NMR (300.1 MHz, CD3CN): d (ppm) 8.49 (d, J =
8.1 Hz, 2H), 8.32 (dd, J = 8.4, 3.0 Hz, 2H), 8.03 (m, 4H), 7.82
(m, 3H), 7.73 (d, J = 5.1 Hz, 1H), 7.59 (s, 1H), 7.35–7.49
(m, 5H), 6.95 (m, 2H), 4.01 (s, 3H), 4.00 (s, 3H), 2.16 (s, 6H).
13C-NMR (75.5 MHz, CD3CN): d (ppm) 151.9, 151.8,
151.5, 151.23, 151.19, 151.0, 137.7, 136.9, 127.0, 126.9,
123.83, 123.78, 122.8, 113.4, 113.3, 110.8, 56.39, 56.35,
17.3, 17.2.
15 Y. Uozumi, A. Tanahashi, S.-Y. Lee and T. Hayashi, J. Org.
Chem., 1993, 58, 1945–1948.
16 For
a related asymmetric synthesis of a chiral octahedral
ruthenium complex by the reaction of complex 2 with a chiral
pentadentate ligand, see: M. Seitz, A. Kaiser, D. R. Powell,
A. S. Borovik and O. Reiser, Adv. Synth. Catal., 2004, 346,
737–741.
IR (film): n (cmꢀ1) 2969, 2927, 1616, 1558, 1494, 1475, 1445,
1420, 1338, 1313, 1279, 1248, 1225, 1046, 1034, 1019, 838, 765,
731, 558, 521, 500, 431, 413.
17 For other examples of the thermal displacement of half-sandwich
moieties with monodentate and bidentate ligands, see for example:
(a) D. A. Freedman, D. E. Janzen and K. R. Mann, Inorg. Chem.,
2001, 40, 6009–6016; (b) X. L. Lu, J. J. Vittal, E. R. T. Tiekink,
G. K. Tan, S. L. Kuan, L. Y. Goh and T. S. A. Hor, J. Organomet.
Chem., 2004, 689, 1978–1990; (c) S. Y. Ng, J. Tan, W. Y. Fan,
W. K. Leong, L. Y. Goh and R. D. Webster, Eur. J. Inorg. Chem.,
2007, 3827–3840; (d) S. Y. Ng, W. K. Leong, L. Y. Goh and
R. D. Webster, Eur. J. Inorg. Chem., 2008, 144–151.
18 D. R. Robertson, I. W. Robertson and T. A. Stephenson,
J. Organomet. Chem., 1980, 202, 309–318.
CD (MeCN): l, nm (De, Mꢀ1 cmꢀ1) 274 (ꢀ48), 294 (+112).
HRMS calcd for RuN6O2C34H32PF6 (M ꢀ PF6)+ 803.1267,
found: 803.1264.
Computational details
The geometry optimizations and frequency calculations of
L-(R)-3 and D-(R)-3 were carried out using the M0523 functional
in conjunction with a def2-SVP24 basis set as implemented in
Gaussian09.25 CPCM-SCRF26 calculations were performed
using a dielectric constant of 37.219 for N,N-dimethylform-
amide to estimate the solvation effect. In CPCM, the choice of
cavities is important because the computed energies and
properties depend on the cavity size. In this study, the UFF
was used, which uses radii from the UFF force field.27
19 D. A. Freedman, J. K. Evju, M. K. Pomije and K. R. Mann, Inorg.
Chem., 2001, 40, 5711–5715.
20 For previous reports of ligand substitutions under retention of the
metal-centered configuration, see: (a) T. J. Rutherford,
M. G. Quagliotto and F. R. Keene, Inorg. Chem., 1995, 34,
3857–3858; (b) X. Hua and A. von Zelewsky, Inorg. Chem., 1995,
34, 5791–5797; (c) D. Hesek, Y. Inoue, S. R. L. Everitt, H. Ishida,
M. Kunieda and M. G. B. Drew, Chem. Commun., 1999, 403–404;
(d) H. Chao, J.-G. Liu, C.-W. Jiang, L.-N. Ji, X.-Y. Li and
C.-L. Feng, Inorg. Chem. Commun., 2001, 4, 45–48; (e) M. Brissard,
O. Convert, M. Gruselle, C. Guyard-Duhayon and R. Thouvenot,
Inorg. Chem., 2003, 42, 1378–1385.
Acknowledgements
We thank the Deutsche Forschungsgemeinschaft for support
of this project.
21 R. A. Zelonka and M. C. Baird, Can. J. Chem., 1972, 50,
3063–3072.
22 Y.-Q. Jiang, Y.-L. Shi and M. Shi, J. Am. Chem. Soc., 2008, 130,
7202–7203.
23 (a) Y. Zhao, N. E. Schultz and D. G. Truhlar, J. Chem. Theory
Comput., 2006, 2, 364–382; (b) Y. Zhao and D. G. Truhlar, Acc.
Chem. Res., 2008, 41, 157–167.
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