Dimethylcuprate undergoes a dyotropic rearrangement

Chemistry - A European Journal

Volumn 16, Issue 9, 2010, Pages 2674-2678

  Rijs, Nicole J ^a,b   Yates, Brian F ^c   O'Hair, Richard A J ^a,b  

^a UNIVERSITY OF MELBOURNE   (Australia)

^b UNIVERSITY OF MELBOURNE   (Australia)

^c UNIVERSITY OF TASMANIA   (Australia)

Author keywords

Copper; Insertion reactions; Organometallic compounds; Reaction mechanisms; Rearrangement

Indexed keywords

AB INITIO CALCULATIONS; GAS-PHASE DECOMPOSITION; HOMOLYSIS; HOMOLYTIC BONDS; INSERTION REACTIONS; ORGANOMETALLIC COMPOUNDS; REACTION MECHANISM; REACTION MECHANISMS;

ORGANOMETALLICS;

ACTIVATION ENERGY;

DEUTERIUM; DIMETHYLCUPRATE(I); ORGANOMETALLIC COMPOUND;

ALGORITHM; ARTICLE; CHEMISTRY; MASS SPECTROMETRY;

ALGORITHMS; DEUTERIUM; MASS SPECTROMETRY; ORGANOMETALLIC COMPOUNDS;

EID: 77149159069     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200903510     Document Type: Article

References (51)

1. a) Modern Organocopper Chemistry (Ed.: N. Krause), Wiley-VCH, Weinheim, 2002;
2. b) Metal-Catalyzed Cross-Coupling Reactions, 2nd ed. (Eds.: A. de Meijere, F. Diederich), Wiley-VCH, Weinheim, 2004.
3. For examples of reductive elimination reactions of well defined copper cluster compounds, see: a) A. Cairncross, W. A. Sheppard, J. Am. Chem. Soc. 1971, 93, 247;
4. b) G. van Koten, J. G. Noltes, J. Chem. Soc. Chem. Commun. 1974, 575.
5. D. S. Surry, D. R. Spring, Chem. Soc. Rev. 2006, 35, 218.
6. a) P. Kocienski, C. Barber, Pure Appl. Chem. 1990, 62, 1933;
7. b) A. Inoue, J. Kondo, H. Shinokubo, K. Oshima, J. Am. Chem. Soc. 2001, 123, 11109;
8. c) J. Kondo, Y. Ito, H. Shinokubo, K. Oshima, Angew. Chem. 2004, 116, 108 -110;
9. Angew. Chem. Int. Ed. 2004, 43, 106 - 108;
10. d) J. Kondo, H. Someya, H. Kinoshita, H. Shinokubo, H. Yorimitsu, K. Oshima, Org. Lett. 2005, 7, 5713.
11. M. T. Reetz, Angew. Chem. 1972, 84, 161;
12. Angew. Chem. Int. Ed. Engl. 1972, 11, 129.
13. For reviews on dyotropic rearrangements, see: a) M. T. Reetz, Adv. Organomet. Chem. 1977, 16, 33;
14. b) I. Fernandez, F. P. Cossio, M. A. Sierra, Chem. Rev. 2009, 109, 6687;
15. c) I. D. Gridnev, Coord. Chem. Rev. 2008, 252, 1798.
16. There are several examples of this type of reaction involving different metals. See, for example: a) E. Negishi, K. Akiyoshi, J. Am. Chem. Soc. 1988, 110, 646;
17. b) V. K. Aggarwal, K. Sommer in The Chemistry of Organozinc Compounds, Part 2 (Eds.: Z. Rappoport, I. Marek), Wiley, New York, 2006, Chapter 13, p. 595.
18. For a review, see: R. A. J. O'Hair, Chem. Commun. 2006, 1469.
19. For bimolecular examples, see: a) P. F. James, R. A. J. O'Hair, Org. Lett. 2004, 6, 2761;
20. b) G. N. Khairallah, R. A. J. O'Hair, Angew. Chem. 2005, 117, 738;
21. Angew. Chem. Int. Ed. 2005, 44, 728;
22. c) G. N. Khairallah, R. A. J. O'Hair, Dalton Trans. 2008, 2956;
23. d) F. Q. Wang, G. N. Khairallah, R. A. J. O'Hair, Int. J. Mass Spectrom. 2009, 283, 17;
24. e) G. N. Khairallah, T. Waters, R. A. J. O'Hair, Dalton Trans. 2009, 2832.
25. For unimolecular examples, see: a) F. Q. Wang, G. N. Khairallah, G. A. Koutsantonis, C. M. Williams, D. L. Callahan, R. A. J. O'Hair, Phys. Chem. Chem. Phys. 2009, 11, 4132;
26. b) C. Thum, G. N. Khairallah, R. A. J. O'Hair, Angew. Chem. 2008, 120, 9258;
27. Angew. Chem. Int. Ed. 2008, 47, 9118.
28. Gaussian 03, Revision E.01, 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.
29. a) N. Rijs, T. Waters, G. N. Khairallah, R. A. J. O'Hair, J. Am. Chem. Soc. 2008, 130, 1069;
30. b) N. J. Rijs, R. A. J. O'Hair, Organometallics 2009, 28, 2684.
31. -•C: R=Ph and M= Cu and Ag, see: a) X.-J. Liu, X. Zhang, K.-L. Han, X.-P. Xing, S.-T. Sun, Z.-C. Tang, J. Phys. Chem. A 2007, 111, 3248 - 3255;
32. b) X.-J. Liu, C.-L. Yang, X. Zhang, K.-L. Han, Z.-C. Tang, J. Comput. Chem. 2008, 29, 1667 -1674;
33. R=CN and M=Cu and Ag, see: c) A. I. Boldyrev, X. Li, L.-S. Wang, J. Chem. Phys. 2000, 112, 3627.
34. These atomic metal anions are stable in the gas phase, see: a) J. Ho, K. M. Ervin, W. C. Lineberger, J. Chem. Phys. 1990, 93, 6987 - 7002;
35. b) H. Handschuh, C.-Y. Cha, P. S. Bechthold, G. Gantefoer, W. Eberhardt, J. Chem. Phys. 1995, 102, 6406.
36. - is as it is a symmetry forbidden process: B. Akermark, A. Ljungqvist, J. Organomet. Chem. 1979, 182, 59.
37. -, see: a) L. Andrews, X. Wang, J. Am. Chem. Soc. 2003, 125, 11751;
38. b) X. Wang, L. Andrews, Angew. Chem. 2003, 115, 5359;
39. Angew. Chem. Int. Ed. 2003, 42, 5201.
40. 1,2-Alkyl migrations have been observed in organometallic cations. For gas-phase examples, see: R. Georgiadis, E. R. Fisher, P. B. Armentrout, J. Am. Chem. Soc. 1989, 111, 4251.
41. For another example of this type of organometallic decomposition, see: A. B. Charette, J.-F. Marcoux, J. Am. Chem. Soc. 1996, 118, 4539.
42. a) T. Aase, M. Tilset, V. D. Parker, J. Am. Chem. Soc. 1990, 112, 4974 - 4975;
43. b) M. J. Hostetler, R. G. Bergman, J. Am. Chem. Soc. 1992, 114, 7629.
44. J. P. Collman, L. S. Hegedus, J. R. Norton, R. G. Finke, Principles and Applications of Organotransition Metal Chemistry, University Science Books, Mill Valley, 1987, p. 381.
45. Copper carbene(I) complexes have been implicated in catalysis and have been isolated. For lead references, see: a) W. Kirmse, Angew. Chem. 2003, 115, 1120;
46. Angew. Chem. Int. Ed. 2003, 42, 1088;
47. b) C. Sivasankar, C. Baskaran, A. G. Samuelson, J. Chem. Sci. 2006, 118, 237.
48. Metal carbenes have often been invoked in Fischer-Tropsch chemistry. For a recent review on late metal carbenes complexes, see: M. T. Whited, R. H. Grubbs, Acc. Chem. Res. 2009, 42, 1607.
49. - is an important product (see Figure S7 in the Supporting Information). Energy resolved CID experiments on this instrument also show that the signal of does not decrease at increasing collision energies (see Figure S8 in the Supporting Information).
50. All electron calculations suggest that the use of an ECP for Cu is not the source of this discrepancy.
51. T. Waters, R. A. J. O'Hair, A. G. Wedd, J. Am. Chem. Soc. 2003, 125, 3384.