Crystal Structure of an η2-Acetonitrile Complex of Tungsten(II): Acetonitrile as a Four-Electron Donor

Journal of the American Chemical Society

Volumn 113, Issue 21, 1991, Pages 8178-8180

  Barrera, Joseph ^a   Sabat, Michal ^a   Harman, W Dean ^a  

^a UNIVERSITY OF VIRGINIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0040734471     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00021a060     Document Type: Article

References (22)

1. Storhoff, B. N.; Lewis, H. C. Coord. Chem. Rev. 1977, 23, 1.
2. Anderson, S. J.; Wells, F. J.; Wilkinson, G.; Hussain, B.; Hursthouse, M. B. Polyhedron 1988, 7(24), 2615.
3. Chetcuti, P. A.; Knobler, C. B.; Hawthorne, M. F. Organometallics 1988, 7, 650.
4. Wright, T. C.; Wilkinson, G.; Motevalli, M.; Hursthouse, M. B. J. Chem. Soc., Dalton Trans. 1986, 2017.
5. T1PF6 (0.0645 g, 0.185 mmol) was added to W(PMe3)2(bpy)Cl2 (0.104 g, 0.185 mmol) in 5 mL of acetonitrile and stirred at room temperature for 5 h. The solution was filtered through Celite and the acetonitrile removed in vacuo. The resulting solid was dissolved in acetone (3 mL), and upon the slow addition of H2O a precipitate formed, which was filtered and dried in vacuo (0.088 g, 67%).
6. Crystal data: C18H23C1F6N3P3W; monoclinic, P21/c (No. 14), a = 14.932 (3) Å, b = 10.138 (4) Å,c= 17.271 (4) Å,β= 107.26 (2)°, V = 2497 (2) Å3, Z = 4. The structure was solved by Patterson and Fourier techniques (TEXSAN 5.0) and refined to R(F) and KW(F) of 0.026 and 0.039, respectively, by using 3687 absorption-corrected reflections with I > 3σ(I) measured on a Rigaku AFC6S diffractometer at -120 °C (Mo Ko radiation, λ = 0.71069 k).
7. Morrow, J. R.; Tonker, T. L.; Templeton, J. L. J. Am. Chem. Soc. 1985, 107, 6956.
8. Karakida, L.; Fukuyama, T.; Kuchitsu, K. Bull. Chem. Soc. Jpn. 1974, 47, 299.
9. Andrews, M. A.; Knobler, C. B.; Kaesz, H. D. J. Am. Chem. Soc. 1979, 101, 7260.
10. Ittel, S. D.; Ibers, J. A. Adv. Organomet. Chem. 1976, 14, 33.
11. For review of trans influence, see; Cotton, F. A.; Wilkinson, G. Advanced Inorganic Chemistry, 4th ed.; John Wiley & Sons: New York, 1980; p 1199.
12. McDonald, J. W.; Newton, W. E.; Creedy, C. T. C.; Corbin, J. L. J. Organomet. Chem. 1975, 97, 1970.
13. Morrow, J. R.; Tonker, T. L.; Templeton, J. L. J. Am. Chem. Soc. 1985, 107, 6956.
14. Keeping with convention, π⊥ and π∥, represent π-orbitals which are perpendicular or parallel, respectively, to the metal—nitrile bond axis.
15. Nakamoto, K. In Infrared and Raman Spectra of Inorganic and Coordination Compounds; J. Wiley and Sons: New York, 1986.
16. 1H NMR (24 °C, acetone-d6): 9.63 (d), 8.78 (d), 8.67 (d), 8.19 (t), 7.68 (t), 7.00 (t), 6.82 (t), 6.46 (d) (bpy, 1 H each); 4.14 (CH3CN, s, 3 H), 1.18 (PMe3, t, 18 H). 13C{1H} NMR (acetone-d6): 235 (t, JCP = 52.8 Hz, CN), 152.3, 149.3, 148.3, 142.4, 140.4, 138.6, 124.9, 123.7, 122.1, 121.9 (s, bpy), 24.0 (s, MeC), 13.1 (t, Jcp = 53.4 Hz, PMe3). Anal. Calcd for WC18H29,N3P3C1F6: C, 30.29; H, 4.10; N, 5.89. Found: C, 30.30; H, 4.08; N, 5.70.
17. Ward, B. C.; Templeton, J. L. J. Am. Chem. Soc. 1980, 102, 1532.
18. Templeton, J. L.; Ward, B. C. J. Am. Chem. Soc. 1980, 102, 3288.
19. Armstrong, E. M.; Baker, P. K.; Drew, M. G. B. Organometallics 1988, 7, 319.
20. Baker, P. K.; Drew, M. G. B.; Flower, K. R. J. Organomet. Chem. 1990, 391, C12.
21. Cyclic voltammograms were recorded in N,N-dimethylacetamide (100 mV s−1/TBAH) for [1]PF6 and W(bpy)(PMe3)2Cl2, the latter showing a W(II/I) couple with E1/2 = −2.21 V (Fc+/Fc).
22. After 15 h in CD3CN at 53 °C, an NMR spectrum of [1]+ shows no detectable substitution. At higher temperatures partial decomposition occurs.