Molecular structures of THF-solvated alkali-metal 2,2,6,6- tetramethylpiperidides finally revealed: X-ray crystallographic, DFT, and NMR (including DOSY) spectroscopic studies

Chemistry - A European Journal

Volumn 17, Issue 24, 2011, Pages 6725-6730

  Armstrong, David R ^a   García ÃÁlvarez, Pablo ^a   Kennedy, Alan R ^a   Mulvey, Robert E ^a   Robertson, Stuart D ^a  

^a UNIVERSITY OF STRATHCLYDE   (United Kingdom)

Author keywords

alkali metals; amides; crystal structures; density functional calculations; NMR spectroscopy

Indexed keywords

CONCENTRATION-DEPENDENT; CYCLIC DIMERS; DENSITY-FUNCTIONAL CALCULATIONS; DFT STUDY; LITHIUM AMIDE; LOW CONCENTRATIONS; NMR SPECTROSCOPY; PLANAR METAL; SODIUM AMIDE; SOLUTION CHEMISTRY; SPECTROSCOPIC STUDIES; THF LIGANDS;

AMIDES; DIMERS; LITHIUM; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SODIUM; SPECTROSCOPIC ANALYSIS; X RAY CRYSTALLOGRAPHY;

METALS;

EID: 79957960294     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201100523     Document Type: Article

References (59)

1. M. F. Lappert, M. J. Slade, A. Singh, J. L. Atwood, R. D. Rogers, R. Shakir, J. Am. Chem. Soc. 1983, 105, 302
2. P. G. Williard, Q.-Y. Liu, J. Am. Chem. Soc. 1993, 115, 3380
3. B. Gehrhus, P. H. Hitchcock, A. R. Kennedy, M. F. Lappert, R. E. Mulvey, P. J. A. Rodger, J. Organomet. Chem. 1999, 587, 88
4. D. R. Armstrong, D. V. Graham, A. R. Kennedy, R. E. Mulvey, C. T. O'Hara, Chem. Eur. J. 2008, 14, 8025.
5. D. Mootz, A. Zinnius, B. Böttcher, Angew. Chem. 1969, 81, 398
6. Angew. Chem. Int. Ed. Engl. 1969, 8, 378
7. R. Grüning, J. L. Atwood, J. Organomet. Chem. 1977, 137, 101
8. L. M. Engelhardt, B. S. Jolly, P. C. Junk, C. L. Raston, B. W. Skelton, A. H. White, Aust. J. Chem. 1986, 39, 1337
9. K. F. Tesh, T. P. Hanusa, J. C. Huffman, Inorg. Chem. 1990, 29, 1584
10. K. W. Henderson, A. E. Dorigo, Q.-Y. Liu, P. G. Williard, J. Am. Chem. Soc. 1997, 119, 11855
11. M. Karl, G. Seybert, W. Massa, K. Harms, S. Agarwal, R. Maleika, W. Stelter, A. Greiner, W. Heitz, B. Neumüller, K. Dehnicke, Z. Anorg. Allg. Chem. 1999, 625, 1301.
12. N. D. R. Barnett, R. E. Mulvey, W. Clegg, P. A. O'Neil, J. Am. Chem. Soc. 1991, 113, 8187
13. M. P. Bernstein, F. E. Romesberg, D. J. Fuller, A. T. Harrison, D. B. Collum, Q.-Y. Liu, P. G. Williard, J. Am. Chem. Soc. 1992, 114, 5100
14. P. G. Williard, J. M. Salvino, J. Org. Chem. 1993, 58, 1
15. P. C. Andrews, N. D. R. Barnett, R. E. Mulvey, W. Clegg, P. A. O'Neil, D. Barr, L. Cowton, A. J. Dawson, B. J. Wakefield, J. Organomet. Chem. 1996, 518, 85
16. W. Clegg, S. Kleditzsch, R. E. Mulvey, P. O'Shaughnessy, J. Organomet. Chem. 1998, 558, 193.
17. R. E. Mulvey, V. L. Blair, W. Clegg, A. R. Kennedy, J. Klett, L. Russo, Nat. Chem. 2010, 2, 588
18. For a rare example where THF is metallated without decomposing see:, A. R. Kennedy, J. Klett, R. E. Mulvey, D. S. Wright, Science 2009, 326, 706.
19. A. Krasovskiy, V. Krasovskaya, P. Knochel, Angew. Chem. 2006, 118, 3024
20. Angew. Chem. Int. Ed. 2006, 45, 2958
21. H. Naka, M. Uchiyama, Y. Matsumoto, A. E. H. Wheatley, M. McPartlin, J. V. Morey, Y. Kondo, J. Am. Chem. Soc. 2007, 129, 1921
22. K. Snégaroff, J.-M. L'Helgoual'ch, G. Bentabed-Ababsa, T. T. Nguyen, F. Chevallier, M. Yonehara, M. Uchiyama, A. Derdour, F. Mongin, Chem. Eur. J. 2009, 15, 10280
23. G. Dayaker, F. Chevallier, P. C. Gros, F. Mongin, Tetrahedron 2010, 66, 8904
24. M. Jeganmohan, P. Knochel, Angew. Chem. 2010, 122, 8699
25. Angew. Chem. Int. Ed. 2010, 49, 8520
26. D. R. Armstrong, P. García-Úlvarez, A. R. Kennedy, R. E. Mulvey, J. A. Parkinson, Angew. Chem. 2010, 122, 3253
27. Angew. Chem. Int. Ed. 2010, 49, 3185
28. for a recent review of complex metalating agents containing an alkali-metal TMP component as part of a heterometallic system see:, R. E. Mulvey, Acc. Chem. Res. 2009, 42, 743.
29. TMP chemistry has recently been extended to calcium:, C. Glock, H. Görls, M. Westerhausen, Inorg. Chem. 2009, 48, 394.
30. F. E. Romesberg, J. H. Gilchrist, A. T. Harrison, D. J. Fuller, D. B. Collum, J. Am. Chem. Soc. 1991, 113, 5751
31. P. L. Hall, J. H. Gilchrist, A. T. Harrison, D. J. Fuller, D. B. Collum, J. Am. Chem. Soc. 1991, 113, 9575
32. B. L. Lucht, D. B. Collum, J. Am. Chem. Soc. 1994, 116, 7949
33. J. F. Remenar, B. L. Lucht, D. Kruglyak, F. E. Romesberg, J. H. Gilchrist, D. B. Collum, J. Org. Chem. 1997, 62, 5748.
34. P. Renaud, M. A. Fox, J. Am. Chem. Soc. 1988, 110, 5702.
35. F. E. Romesberg, D. B. Collum, J. Am. Chem. Soc. 1992, 114, 2112.
36. A search of the Cambridge Crystallographic database for structures containing a THF-solvated lithium cation yields 2134 hits (, F. H. Allen, Acta Crystallogr. Sect. B: Struct. Sci. 2002, 58, 380). For some representative examples of simple THF-solvated lithium alkyl structures see
37. M. A. Nichols, P. G. Williard, J. Am. Chem. Soc. 1993, 115, 1568
38. C. A. Ogle, B. K. Huckabee, H. C. Johnson IV, P. F. Sims, S. D. Winslow, A. A. Pinkerton, Organometallics 1993, 12, 1960
39. T. Kottke, R. J. Lagow, D. Hoffman, R. D. Thomas, Organometallics 1997, 16, 789.
40. -3.
41. -3.
42. 13C INEPT DOSY NMR:, D. Li, R. Hopson, W. Li, J. Liu, P. G. Williard, Org. Lett. 2008, 10, 909.
43. D. Li, I. Keresztes, R. Hopson, P. G. Williard, Acc. Chem. Res. 2009, 42, 270
44. A. Macchioni, G. Ciancaleoni, C. Zuccaccia, D. Zuccaccia, Chem. Soc. Rev. 2008, 37, 479
45. B. Antalek, Concepts Magn. Reson. Part A 2007, 30, 219
46. J. S. Gounarides, A. Chen, M. J. Shapiro, J. Chromatogr. B: Biomed. Sci. Appl. 1999, 725, 79
47. T. Tatic, K. Meindl, J. Henn, S. K. Pandey, D. Stalke, Chem. Commun. 2010, 46, 4562.
48. E. Crosbie, P. García-Úlvarez, A. R. Kennedy, J. Klett, R. E. Mulvey, S. D. Robertson, Angew. Chem. 2010, 122, 9578
49. Angew. Chem. Int. Ed. 2010, 49, 9388.
50. C. Schade, W. Bauer, P. v. R. Schleyer, J. Organomet. Chem. 1985, 295, C 25.
51. Gaussian 03, Revision C.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Wallingford CT, 2004.
52. W. J. Hehre, R. Ditchfield, J. A. Pople, J. Chem. Phys. 1972, 56, 2257
53. P. C. Hariharan, J. A. Pople, Theor. Chim. Acta 1973, 28, 213.
54. W. Kohn, A. D. Becke, R. G. Parr, J. Phys. Chem. 1996, 100, 12974
55. A. D. Becke, Phys. Rev. A 1988, 38, 3098
56. C. T. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785.
57. A. D. McLean, G. S. Chandler, J. Chem. Phys. 1980, 72-73, 5639
58. R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650.
59. G. M. Sheldrick, Acta Crystallogr. Sect. A 2007, 64, 112.