Demonstration of "Möbius" aromaticity in planar metallacycles

Chemistry - A European Journal

Volumn 16, Issue 26, 2010, Pages 7843-7851

  Mauksch, Michael ^a   Tsogoeva, Svetlana B ^a  

^a UNIVERSITY OF ERLANGEN NUREMBERG   (Germany)

Author keywords

Aromaticity; Chemical bonding; Metallacycles; M bius aromaticity; Reaction intermediates

Indexed keywords

ANTIAROMATICITY; AROMATIC STABILIZATION ENERGIES; AROMATICITIES; BINDING MODES; BONDING ANALYSIS; C-C BONDS; CHEMICAL BONDINGS; CYCLIC MOLECULES; CYCLOHEPTATRIENES; D ORBITALS; MAIN-GROUP ELEMENTS; METALLACYCLES; NUCLEUS INDEPENDENT CHEMICAL SHIFTS; ODD NUMBERS; ORBITAL PHASE; PHASE INVERSION; PLANARITY; STABILIZING EFFECTS; TRANSITION STATE; WIBERG BONDS;

AROMATIC COMPOUNDS; BENZENE; BINDING ENERGY; CHEMICAL BONDS; MOLYBDENUM; REACTION INTERMEDIATES; TRANSITION METALS;

AROMATIZATION;

EID: 77954330182     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201000396     Document Type: Article

References (114)

1. a) L. Pauling, The Nature of the Chemical Bond, 3rd ed., Cornell University Press, Ithaca, 1960;
2. b) F. Hund, Z. Phys. 1926, 36, 657;
3. c) R. S. Mulliken, Phys. Rev. 1928, 32,186.
4. E. Heilbronner, Tetrahedron Lett. 1964, 5, 1923.
5. a) M. J. S. Dewar, Angew. Chem. 1971, 83, 859;
6. Angew. Chem. Int. Ed. Engl. 1971, 10, 761;
7. b)H. E. Zimmerman, J. Am. Chem. Soc. 1966, 88, 1564;
8. c) H. E. Zimmerman, Ace. Chem. Res. 1971, 4, 272.
9. Barrelene is an example of a "Möbius" molecule with purely longicydically (σ-type) overlapping p orbitais and an odd number of ring centers. Hence, in one-electron (HMO) theory, it does not show aromatic stabilization as a neutral species, see: H. E. Zimmerman, G. L. Grunewald, R. M. Paufler, M. A Sherwin, J. Am. Chem. Soc. 1969, 91, 2330.
10. For an early experimental attempt to prepare a ground state 4π electron Möbius homoaromatic cation in superacids solutions, see: H. M. J. Guussen, H. M. Buck, J. Org. Chem 1982, 47, 5124.
11. a) Möbius ground state annulene aromaticity, for decades seen as merely hypothetical, was described as "unrealistic": J. Aihara, Bull Chem. Soc. Jpn. 1978, 51, 1788;
12. b) N. Mizoguchi, Chem Phys. Lett. 1987, 134, 371;
13. c) P. Karadakov, V. Enchev, F. Fratev, O. Castano, Chem. Phys. Lett. 1981, 83, 529.
14. d) The concept of "Möbius annulenes" was even seen as harmful for pedagogical reasons: R. F. Langler, J. Chem. Educ. 1996, 73, 899;
15. e) M. J. Goldstein, R. Hoffmann, J. Am. Chem. Soc. 1971, 93, 6193.
16. f) The first recognition of either Möbius or Hiickel character of molecular orbitais in metallacycles was first articulated in: A. J. Kos, P. von R. Schleyer,J. Am. Chem. Soc. 1980,102,7928.
17. +:
18. b) M. Mauksch, V. Gogonea, H. Jiao, P. v. R. Schleyer, Angew. Chem. 1998, 110, 2515;
19. Angew. Chem. Int. Ed. 1998, 37, 2395;
20. S. Martin-Santamaría, B. Lavan, H, S. Rzepa, J. Chem. Soc. Perkin Trans. 2 2000, 1415;
21. d) S. Martin-Santamaría, H. S. Rzepa, Chem. Commun. 2000, 1089;
22. e) S. Martin-Santamaría, H. S. Rzepa, J. Chem. Soc. Perkin Trans. 2 2000, 2372.
23. f) Also see for a later report on. neutral Möbius[4n]annulenes, partly based and expanding on Reference [7a]: C. Castro, C. M. Isborn, W. L. Karney, M. Mauksch, P. v. R. Schleyer, Org. Lett. 2002, 4, 3431.
24. g) See also for Möbius triplet aromaticity and the generalization of aromaticity rules (which include both Möbius triplet and Möbius antiaromaticity), see Reference [7a]: C. J. Kastrup, S. P. Oldfield, H, S. Rzepa, Chem. Commun. 2002, 642;
25. h) P. M. Warner, J. Org. Chem. 2006, 71, 9271.
26. n chirality (n is an odd number, see Ref. [36]) of higher-order twisted charged Möbius annulenes: C. S. Wannere, H.S. Rzepa, B.C. Rinderspacher, A, Paul, C. S. M, Allan, H. F. Schaefer III, P. v. R. Schleyer, J. Phys. Chem. A 2009,113,11619.
27. D. Ajami, O. Oeckler, A. Simon, R. Herges, Nature 2003, 426, 819.
28. a) Y. Tanaka, S. Saito, S. Mori, N. Aratani, H. Shinokubo, N. Shibata, Y. Higuchi, Z. S. Yoon, K. S. Kim, S. B. Noh, J. K. Park, D. Kim, A. Osuka, Angew. Chem. 2008, 120, 693;
29. Angew. Chem Int. Ed. 2008, 47, 681;
30. b) M. Inoue, K. S. Kim, M. Suzuki, J. M. Lin, J. Y. Shin, D. Kim, A. Osuka, Angew. Chem. 2009, 121, 6815;
31. Angew. Chem. Int. Ed. 2009,48, 6687.
32. M, Mauksch, S. B. Tsogoeva, Angew. Chem. 2009, 121, 3003;
33. Angew. Chem. Int. Ed. 2009, 48, 2959.
34. For reviews, see: a) H. S. Rzepa, Chem. Rev. 2005, 105, 3697;
35. b) R. Herges, Chem. Rev. 2006, 106, 4820;
36. c) Z. S. Yoon, A. Osuka, D. Kim, Nat. Chem. 2009, 1, 113.
37. a) C. Castro, W. L. Karney, M, A. Valencia, C. M, H. Vu, R. P. Pemberton, J. Am Chem. Soc. 2005, 127, 9704;
38. b)R.P. Pemberton, C. M. McShane, C. Castro, W. L. Karney, J. Am. Chem. Soc. 2006, 128,16692.
39. a) D. P. Craig, N. L Paddock, Nature 1958, 181, 1052;
40. b) D. P. Craig, J. Chem. Soc. 1959, 997.
41. a) The concept of aromatic metallacycles goes back to Calvin and Wilson: M, Calvin, K. W. Wilson, J. Am Chem. Soc. 1945, 67, 2003;
42. b) for a review, see: H, Masui, Coord. Chem. Rev. 2001,219, 957.
43. a) Rzepa (ref. [11a]), in analogy to earlier theoretical anticipations of Kos and Schleyer for bridged doubly lithiated butadiene (Ref. [6f]), suggested a five-membered vanadacyde with a diiminato ligand as a "6π delocalized system with 2π occupancy of a pπ-dπ Craig/Möbius orbital bearing a localized dπ phase shift at the metal atom". In contrast, we describe herein 8π electron Möbius aromatics with two pairs of MO's of Möbius and Hückel character, respectively, and with the phase inversion across the ring opposite to the metal atom,
44. b) See for transition metal d-orbital involvement in a twisted π-conjugated macrocycle: H. S. Rzepa, Inorg. Chem. 2008, 47, 8932.
45. a) A, G. Wenzel, R. H. Grubbs, J. Am. Chem. Soc. 2006, 128, 16048;
46. b) R. H. Grubbs, Tetrahedron 2004, 60, 7117;
47. c) R. H. Grubbs, A. Miyashita, J. Am. Chem. Soc. 1978, 100, 7416;
48. d) R. R. Schrock, J. Am. Chem. Soc. 1974, 96, 6796;
49. e)T. J. Katz, J. McGinnes, J. Am. Chem. Soc. 1975, 97, 1592;
50. f) F. Erdman III, D. B. Lawson, J. Organomet. Chem. 2005,690,4939.
51. a) W. Reppe, W. J. Schweckendieck, Justus Liebig Ann. Chem. 1948, 560, 93;
52. b) for reviews, see: S. Kotha, E. Brahmachary, K. Lahiri, Eur. J. Org. Chem. 2005, 4741;
53. c) B. R. Galan, T. Rovis, Angew. Chem. 2009, 121, 2870;
54. d) P. R. Chopade, J. Louie, Adv. Synth. Catal. 2006,348, 2307.
55. Y. Yamamoto, H. Takagishi, K. Itoh, Org. Lett 2001, 3, 2117.
56. L. Sripada, J. A. Teske, A. Deiters, Org. Biomol. Chem. 2008, 6, 263.
57. M, Petit, G. Chouraqui, P. Phansavath, C. Aubert, M. Malacria, Org. Lett. 2002, 4,1027.
58. D. L. Thorn, R. Hoffmann, Nouv. J. Chim. 1979,3, 39.
59. G. P. Elliott, W. R. Roper, J. M. Waters, J. Chem. Soc. Chem. Commun. 1982, 811,
60. C. E. F. Rickard, W. R. Roper, S. D. Woodgate, L. J. Wright, Angew. Chem. 2000, 112, 766;
61. Angew. Chem. Int. Ed. 2000, 39, 750.
62. For reviews on metallabenzenes, see: a) J. R. Bleeke, Chem. Rev. 2001, 101, 1205;
63. b)L. J. Wright, Dalton Trans. 2006, 1821;
64. c)C.W. Landorf, M, M. Haley, Angew. Chem. 2006, 118, 4018;
65. Angew. Chem. Int. Ed. 2006, 45, 3914;
66. d) for the first synthesis of iridabenzene: J. R. Bleeke, Acc. Chem. Res. 1991, 24, 271;
67. e) for theoretical investigations, see: Y-Z. Huang, S.-Y. Yang, X.-Y Li, J. Organomet. Chem. 2004, 689, 1050;
68. f)I. Fernández, G. Fren king, Chem. Eur. J. 2007,13, 5873;
69. g) G. Periyasamy, N. A. Burton, I. H. Hillier, J. M. H. Thomas, J. Phys. Chem. A 2008, 112, 5960.
70. a) R. R. Schrock, S. F. Pedersen, M. R. Churchill, J. W. Ziller, Organometallics 1984, 3, 1574;
71. b) R. P. Hughes, H.A. Trujillo, A. L. Rheingold, J. Am. Chem. Soc. 1993, 115, 1583;
72. c) T. M, Sivavec, T. J. Katz, Tetrahedron Lett. 1985,26, 2159.
73. a) N. E. Schore, Chem. Rev. 1988, 88, 1081;
74. b) T. Takahashi, M, Ishikawa, S. Huo, J. Am. Chem. Soc. 2002,124, 388;
75. c) for synthesis of a metallacycloheptatriene, see: M, Paneque, C.M. Posadas, M. L. Pověda, N. Rendón, L. L. Santos, E. Alvarez, V. Salazar, K. Mereiter, E. Oflate,. J. Organomet. Chem. 2003, 682, 204;
76. d) these molecules have been frequently proposed as intermediates in cyclotrimerization of alkynes, for example: K. P. C. Vollhardt, R. G. Bergman, J. Am. Chem. Soc. 1974, 96, 4996;
77. e) D. R. McAlister, J E. Bercaw, R. G. Bergman, J. Am. Chem. Soc. 1977, 99, 1666;
78. f) R. L. Hillard III, K. P. C. Vollhardt, J. Am Chem. Soc. 1977, 99, 4058.
79. The NAOs are, for isolated atoms, identical with the hydrogen-like valence-shell orbitais. In the molecular environment, the natural atomic orbitais are the maximum occupancy "effective" atomic orbitais in a molecule.
80. - ligand.
81. 3] (see Table 1.)
82. G. P. Bean, J. Org. Chem. 1998, 63, 2497.
83. a) P. von R. Schleyer, C. Maerker, A, Dransfeld, H, Jiao, N. van Eikema Hommes, J. Am. Chem. Soc. 1996, 118, 6317;
84. b) for a review, see: Z. Chen, C. S. Wannere, C. Corminboeuf, R. Puchta, P. v. R. Schleyer, Chem. Rev. 2005,105, 3842;
85. H. Fallah-Bagher-Shaidaei, C. S. Wannere, C. Corminboeuf, R. Puchta, P. v. R. Schleyer, Org. Lett. 2006, 8, 863.
86. ZZ = -7.4 for 1, with a different basis set), see Reference [24 g].
87. a) P. von R. Schleyer, F. Pühlhofer, Org. Lett. 2002, 4, 2873;
88. -1, see: F. De Proft, P. Geerlings, Phys. Chem. Chem. Phys. 2004, 6, 242.
89. P. George, C. W. Bock, M, Trachtman, Tetrahedron Lett. 1985, 26, 5667.
90. a) P. W. Fowler, Phys. Chem. Chem. Phys. 2002, 4, 2878;
91. b) for Möbius-Hückel spectra in an example from classical physics: D.J. Ballon, H. U. Voss, Phys. Rev. Lett. 2008, 101, 247701,
92. A recent work proposed that derivatives of neutral l.H-M.öbius aza[l.l.]annulenes could be lower in energy than conformations with the Hückel topology, see: M. Mauksch, S. B. Tsogoeva, Eur. J. Org. Chem. 2008,5755.
93. In cycloheptatetraene was a similar pairing of Hückel and Möbius orbitais computationally found, see Reference [7e].
94. T. Xiang, N. d'Ambrumenil, Phys. Rev. B 1992, 46, 11179.
95. a) J. Kruszewski, T. M, Krygowski, Tetrahedron 1972, 28, 3839;
96. b) T. M, Krygowski, J. Chem. Inf. Comput. Sci. 1993, 33, 70;
97. c) T. M, Krygowski, M. Cyrański, Tetrahedron 1996, 52, 1713;
98. T.M, Krygowski, M, Cyrański, Tetrahedron 1996, 52, 10255;
99. e) for a review see: T. M, Krygowski, M. Cyranski, Chem. Rev. 2001, 101,1385.
100. a) L. Pauling, J. Am. Chem. Soc. 1947, 69, 542.
101. 2) bond, respectively, see Reference [40a], and references therein.
102. K, P. C. Vollhardt, Ace. Chem. Res. 1977,10, 1,
103. a) L. Kloppenburg, D. Jones, U. H. F. Bunz, Macromolecules 1999, 32, 4194.
104. 6 gives a 14VE species that could principally react with alkynyls by oxidative addition.
105. Gatteschi and co-workers reported a true one-dimensional "magnetic" Möbius strip made of an odd-membered cycle of metal atoms in which the incommensurability of unpaired antiferromagnetically coupled electron spins results in "spin frustration": O. Cador, D. Gatteschi, R. Sessoli, A.-L. Barra, G. A. Timco, R. E. P. Winpenny, J. Magn. Magn. Mater. 2005,290, 55.
106. V. Gogonea, P. v. R. Schleyer, P. Schreiner, Angew. Chem, 1998, 110, 2045;
107. Angew. Chem. Int. Ed. 1998, 37,1945.
108. M, Nihei, T. Shiga, Y Maeda, H. Oshio, Coord, Chem. Rev. 2007, 25.7, 2606.
109. -1 higher in energy than the singlet.
110. Gaussian 03, Revision A.11.4, M.J. Frisch, G.W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M, Millam, A. D. Daniels, K, N. Kudin, M, C. Strain, O. Farkas, J. Tomasi, V. Barone, M, Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, X Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, N. Rega, P. Salvador, J. J. Dannenberg, D. K. Malick, A. D. Rabuck, K, Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, 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, J. L. Andres, C. Gonzalez, M, Head-Gordon, E. S. Replogle, and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 2002.
111. D. Andrae, U. Häussermann, M. DoIg, H, Stoll, H, Preuss, Theor. Chem. Ace. 1990, 77, 123.
112. J. H. Wood, A. M. Boring, Phys. Rev. B 1978,18, 2701.
113. A. D. Becke, / Chem. Phys. 1993, 98, 1372.
114. C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785.