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http://dx.doi.org/10.5012/bkcs.2003.24.5.605

Synthesis and Characterization of (THF)3 Li(NC)CU(C6H3-2,6-Mes2)and Br(THF)2 Mg(C6H3-2,6-Trip2) (Mes = C6H2-2,4,6-Me3; Trip = C6H2-2,4,6-i-Pr3): The Structures of a Monomeric Lower-Order Lithi  

Hwang, Cheong-Soo (Department of Chemistry, Dankook University)
Power, Philip P. (Department of Chemistry, University of California)
Publication Information
Bulletin of the Korean Chemical Society / v.24, no.5, 2003 , pp. 605-609 More about this Journal
Abstract
The lower-order lithium organocyanocuprate compound, (THF)₃Li(NC)Cu($C_6$H₃-2,6-Mes₂) (1), and the bulky terphenyl Grignard reagent, Br(THF)₂Mg($C_6$H₃-2,6-Trip₂) (2), have been synthesized and structurally characterized both in the solid state by single crystal x-ray crystallography and in solution by multi-nuclear NMR and IR spectroscopy. The compound (1) was isolated as a monomeric contact ion-pair in which the C (organic ipso)-Cu-CN-Li atoms are coordinated linearly. The lithium has a tetrahedral geometry as a result of solvation by three THF molecules. The compound (1) is the first example of fully characterized monomeric lower order lithium organocyanocuprate. The bulky Grignard reagent (2) was also isolated as a monomer in which the magnesium, solvated by two THF molecules, has a distorted tetrahedral geometry. The crystals of (1) possess triclinic symmetry with the space group $P{\={1}}$, Z = 2, with a = 12.456(3) Å, b = 12.508(3) Å, c = 13.904(3) Å, α = 99.81°, β = 103.72(3)°, and γ = 119.44(3)°. The crystals (2) have a monoclinic symmetry of space group $P2_{1/C}$, Z = 4, with a = 13.071(3) Å, b = 14.967(3) Å, c = 22.070(4) Å, and β = 98.95(3)°.
Keywords
Cyanocuprate; Organocopper; Grignard reagent; Terphenyl ligand;
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1 Lipshutz, B. H.; Wilhelm, R. S.; Kozlowsky, J. A. Tetrahedron1984, 40, 5005   DOI   ScienceOn
2 Lipshutz, B. H.; Kozolowski, J. A.; Wilhelm, R. S. J. Org. Chem.1984, 49, 3943.   DOI
3 Barnhart, T. M.; Huang, H.; Penner-Hahn, J. E. J. Org. Chem. 1995, 60, 4310.   DOI   ScienceOn
4 Huang, H.; Alvarez, K.; Lue, Q.; Barnhart, T. M.; Snyder, J. P.;Penner-Hahn, J. E. J. Am. Chem. Soc. 1996, 118, 8808.   DOI   ScienceOn
5 Kronenberg, C. M. P.; Jastrzebski, J. T. B. H.; Spek, A. L.; vanKoten, G. J. Am. Chem. Soc. 1998, 120, 9688.   DOI   ScienceOn
6 Haaland, A.; Rypdal, K.; Verne, H. P.; Scherer, W.; Thiel, W. R.Angew. Chem., Int. Ed. Engl. 1994, 33, 2443.   DOI   ScienceOn
7 Hope, H. A. Practicum in Synthesisand Characterization in Experimental Organometallic Chemistry;Wayda, A. L., Darensbourg, M. Y., Eds.; ACS symposium Series357; American Chemical Society: Washington D. C., 1987;Chapter 10.
8 Ellison, J. J.; Power, P. P. J. Organomet. Chem. 1996, 526, 263.   DOI   ScienceOn
9 Gorlier, J.-P.; Hamon, L.; Levisalles, J.; Wagon, J. J. Chem. Soc., Chem. Commun. 1973, 88.
10 Hwang, C.-S.; Power, P. P. J. Organomet. Chem. 1999, 589, 234.   DOI   ScienceOn
11 Lingnau, R.; Strähle, J. Angew. Chem., Int. Ed. Engl. 1988, 27, 436.   DOI
12 House, H. O.; Umen M. J. J. Org. Chem. 1973, 38, 3893.   DOI
13 Noltes, J. G.; van Koten, G. In Comprehensive Organometallic Chemistry; Pergamon: Oxford, 1982; Vol. 2, Chapter 14, p 709.
14 van Koten, G.; James, S. L.; Jastrzebski, J. T. B. H. In Comprehensive Organometallic Chemistry II; Elsevier: Amsterdam, 1995; Vol. 3, Chapter 2, p 57
15 Corey, E. J.; Posner, G. H. J. Am. Chem. Soc. 1967, 89, 3911.
16 Corey, E. J.; Beames, D. J. J. Am. Chem. Soc. 1972, 94, 7210.   DOI
17 Bransma, L.; Verkruijsse, H. Preparative Polar Organometallic Chemistry; Trost, B. M., Ed.; Springer-Verlag: New York, 1986; Vol 1.
18 Lipshutz, B. H.; Sharma, S.; Ellsworth, E. L. J. Am. Chem. Soc. 1990, 12, 4032.
19 Boche, G.; Bosold, F.; Marsch, M.; Harms, K. Angew. Chem.1998, 110, 1779.   DOI   ScienceOn
20 He, X.; Olmstead, M. M.; Power, P. P. J. Am. Chem. Soc. 1992,114, 9668.   DOI
21 Ruhlandt-Senge, K.; Ellison, J. J.; Wehmschulte, R. J.; Pauer, F.;Power, P. P. J. Am. Chem. Soc. 1993, 115, 11353.   DOI   ScienceOn
22 Kohler, E. P.; Blanchard, L. W. J. Am. Chem. Soc. 1935, 57, 367.   DOI
23 Cotton, F. A.; Wilkinson, G. In Advanced Inorganic Chemistry, 5th Ed.; John Wiley & Sons: 1988; Chapters 4 and 5.
24 Bertz, S. H.; Fairchild, E. H. In Reagents for Organic Synthesis; Paquette, L., Ed.; Wiley: New York, 1995; p 1341
25 Snyder, J. P.; Bertz, S. H. J. Org. Chem. 1995, 60, 4312.   DOI   ScienceOn
26 Lindsell, W. E. In Comprehensive Organometallic Chemistry; Pergamon: Oxford, 1981; Vol. 1, Chapter 4.
27 Snyder, J. P.; Spangler, D. P.; Behling, J. R.; Rossiter, B. J. Org.Chem. 1994, 59, 2665.   DOI   ScienceOn
28 Rieke, R. D.; Li, P. T.; Burns, T. P.; Uhm, S. T. J. Org. Chem.1981, 46, 4323.   DOI
29 Lipshutz, B. H.; Wilhelm, R. S.; Floyd, D. M. J. Am. Chem. Soc.1981, 103, 7672.   DOI
30 SHELXTL, A Program for Crystal Structure Determinations, v.5.03; Siemens Analytical Instrument: Madison, WI, 1994.
31 Bertz, S. H. J. Am. Chem. Soc. 1991, 113, 5470.   DOI
32 Silverman, G. S.; Rakita, P. E. Handbook of Grignard Reagents;Marcel Dekker, Inc.: 1996; Chapter 1.
33 Parkin, S. R.; Moezzi, B.; Hope, H. J. Appl. Cryst. 1995, 28, 53.   DOI   ScienceOn
34 Eaborn, C.; Hill, M. S.; Hitchcock, P. B.; Smith, J. D.Organometallics 2000, 19, 5780.   DOI   ScienceOn
35 Boche, G.; Bosold, F.; Marsch, M.; Harms, K. Angew. Chem., Int. Ed. 1998, 37, 1684.   DOI   ScienceOn
36 Setzer, W.; Schleyer, P. V. R. Adv. Organomet. Chem. 1985, 24,353.   DOI
37 Stemmler, T. J.; Barnhart, T. M.; Penner-Hahn, J. E.; Tucker, C.E.; Knochel, P.; Bohme, G.; Frenking, G. J. Am. Chem. Soc. 1995,117, 12489.   DOI
38 Haubrich, S. T.; Power, P. P. J. Am. Chem. Soc. 1998, 120, 2202.   DOI   ScienceOn
39 Bertz, S. H. J. Am. Chem. Soc. 1990, 12, 4031
40 Schiemenz, B.; Power, P. P. Organometallics 1996, 15, 958.   DOI   ScienceOn
41 Krause, N. Angew. Chem., Int. Ed. Engl. 1999, 38, 79.   DOI   ScienceOn
42 Hwang, C.-S.; Power, P. P. J. Am. Chem. Soc. 1998, 120, 6409.   DOI   ScienceOn
43 Stemmler, T. J.; Penner-Hahn, J. E.; Knochel, P. J. Am. Chem.Soc. 1993, 115, 348.   DOI
44 Pauer, F.; Power, P. P. In Lithium Chemistry- A Theoreticaland Experimental Overview; Sapse, A.-M., Schleyer, P. V. R.,Eds.; Wiley: New York, 1985; Chapter 9, p 295.
45 Hwang, C.-S.; Power, P. P. Organometallics 1999, 18, 697.   DOI   ScienceOn