3,3′,5,5′-Tetrapyridylbiphenyl: A Biscyclometalating Bridging Ligand with a High Coupling Ability in Ru111,Ru11 Mixed Valence Systems

Journal of the American Chemical Society

Volumn 113, Issue 22, 1991, Pages 8521-8522

  Beley, Marc ^a   Collin, Jean Paul ^a   Louis, Rèmy ^a   Sauvage, Jean Pierre ^a   Metz, Bernard ^a  

^a UNIVERSITÉ DE STRASBOURG   (France)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0040431276     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00022a049     Document Type: Article

References (14)

1. Balzani, V.; Scandola, F. Supramolecular Chemistry; Ellis Horwood: Chichester, 1991 and references.
2. Creutz, C.; Taube, H. J. Am. Chem. Soc. 1969, 91, 3988–3989.
3. Creutz, C. Prog. Inorg. Chem. 1983, 30, 1–73.
4. Richardson, D. E.; Taube, H. Coord. Chem. Rev. 1984, 60, 107–129.
5. Sutton, J. E.; Taube, H. Inorg. Chem. 1981, 20, 3125–3134.
6. Powers, M. J.; Meyer, T. J. J. Am. Chem. Soc. 1980, 102, 1289–1297.
7. Krentzien, H.; Taube, H. J. Am. Chem. Soc. 1976, 98, 6379–6880.
8. Harman, W. D.; Taube, H. J. Am. Chem. Soc. 1987, 109, 1883–1885.
9. dpb-H was prepared according to a synthetic method previously described for 2,2′-(l,4-phenylene)dipyridine.9 1,3-Dicyanobenzene (4 g; 32.2 mmol) and Co(Cp)COD (0.1 g; COD is 1,5-cyclooctadiene) dissolved in 40 mL of toluene were loaded in an autoclave under 10 atm of acetylene. The autoclave was heated to 130 °C for 3 days. After workup and chromatography (silica; CH2Cl2–CH3OH as eluent), dpb-H was obtained as a colorless oil (6.5 g; 90%). 1H NMR (200 MHz, CD2CI2):5 8.7 (m, 3 H), 8.09 (d, 2 H, 2 Hz), 8.06 (dd, 2 H, 2 Hz), 7.85 (m, 4 H), 7.58 (t, 1 H, 8 Hz), 7.27 (ddd, 2 H, 7, 4, 1.5 Hz). MS: m/z = 232; C16H,2N2 requires 232.
10. Bonnemann, H. Angew. Chem., Int. Ed. Engl. 1978, 17, 505–515.
11. Ru(tterpy)(dpb)+(PF6−): 1H NMR (200 MHz, CD3CN) 5 8.98 (s, 2 H), 8.55 (d, 2 H, 8 Hz), 8.25 (d, 2 H, 8 Hz), 8.16 (m, 4 H), 7.70 (td, 2 H, 8, 2 Hz), 7.56 (m, 4 H), 7.45 (t, 1 H, 8 Hz), 7.09 (m, 4 H), 6.94 (m, 2 H), 6.65 (m, 2 H), 2.51 (s, 3 H); FAB-MS (nitrobenzyl alcohol matrix) m/z-656.1, Ru(tterpy)(dpb)+ requires 656. [Ru(tterpy)]2(tpbp)2+(PF6−)2: 1H NMR (200 MHz, CD3CN) й 9.05 (s, 4 H), 8.97 (s, 4 H), 8.62 (d, 4 H, 8 Hz), 8.48 (d, 4 H, 8 Hz), 8.14 (d, 4 H, 8 Hz), 7.78 (d, 4 H, 8 Hz), 7.70 (d, 4 H, 8 Hz), 7.57 (d, 4 H, 8 Hz), 7.30 (d, 4 H, 6 Hz), 7.18 (d, 4 H, 6 Hz), 7.04 (t, 4 H, 6 Hz), 6.73 (t, 4 H, 6 Hz), 2.53 (s, 6 H); FAB-MS (nitrobenzyl alcohol matrix) m/z = 1455.2, [Ru2(tterpy)2(tpbp)(PF6)]+ requires 1455.
12. The compound [Ru2(tterpy)2(tpbp)](PFs)2-(CH3)2CO crystallized in the monoclinic space group P21/n, a = 22.464 (3) Å, b = 17.834 (2) Å, c = 20.107 (2) Å, β = 98.72 (1)°, V= 7962 (3) Å3, μ(CU K∝) = 41.86 cm−1 and DCALCD =1-38 g-cm−3 for Z = 4, Ru2F12ON10C79H60 MW = 1657.5. Reflections were measured on an Enraf-Nonius CAD 4 diffractometer using Cu Ka graphitemonochromated radiation (ω/2θ scan mode, scan width (ω) 0.55 + 0.14 tan θ,4° < θ < 59°). The compound is unstable at room temperature, due to a loss of acetone; 11 264 unique data, 7458 with I > 3<б(I). A decay correction and an empirical absorption correction (ψ scan) were applied. The non-hydrogen atoms were located by direct methods and refined anisotropically. The hydrogen atoms except those of the acetone molecule were included as idealized contributions. Actual R = 0.067 and Rw = 0.121. All calculations were done with SDP (Structure Determination Package; B. A. Frenz and Associates Inc., College Station, TX, and Enraf-Nonius, Delft, 1983). Diffraction and calculation work was performed at Laboratoire de Cristallographie Biologique, IBMC, Strasbourg.
13. Callahan, W. H.; Keene, F. R.; Meyer, T. J.; Salmon, D. J. J. Am. Chem. Soc. 1977, 99, 1064–1073.
14. Hush, N. S. Prog. Inorg. Chem. 1967, 8, 391.