Pentagerma[1.1.1]propellane: A combined experimental and quantum chemical study on the nature of the interactions between the bridgehead atoms

Angewandte Chemie - International Edition

Volumn 48, Issue 8, 2009, Pages 1411-1416

  Nied, Dominik ^a   Klopper, Wim ^a   Breher, Frank ^a  

^a UNIVERSITY OF KARLSRUHE   (Germany)

Author keywords

Biradicaloid species; Cluster compounds; Density functional calculations; Germanium; Metallapropellanes

Indexed keywords

ATOMIC PHYSICS; ATOMS; GERMANIUM; QUANTUM CHEMISTRY;

BIRADICALOID SPECIES; BONDING PROPERTIES; CAS-SCF; CLUSTER COMPOUNDS; DENSITY FUNCTIONAL CALCULATIONS; METALLAPROPELLANES; PROPELLANE; QUANTUM CHEMICAL STUDIES; REDOX CHEMISTRIES;

DENSITY FUNCTIONAL THEORY;

EID: 60149112597     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200805289     Document Type: Article

References (67)

1. a) F. Breher, Coord. Chem. Rev. 2007, 251, 1007;
2. b) M. Karni, Y. Apeloig, J. Kapp, P. von R. Schleyer in The Chemistry of Organic Silicon Compounds, Vol. 3 (Eds.: Z. Rappoport, Y. Apeloig), Wiley, Chichester, 2001.
3. K. B. Wiberg, Chem. Rev. 1989, 89, 975.
4. a) M. Messerschmidt, S. Scheins, L. Grubert, M. Pätzel, G. Szeimies, C. Paulmann, P. Luger, Angew. Chem. 2005, 117, 3993;
5. Angew. Chem. Int. Ed. 2005, 44, 3925;
6. b) P. Coppens, Angew. Chem. 2005, 117, 6970; Angew. Chem. Int. Ed. 2005, 44, 6810.
7. a) W. Wu, J. Gu, J. Song, S. Shaik, P. C. Hiberty, Angew. Chem. 2009, DOI: 10.1002/ange.200804965; Angew. Chem. Int. Ed. 2009, DOI: 10.1002/anie.200804965; For a nice explanation of "charge-shift bonding" in general, see
8. b) S. Shaik, D. Danovich, B. Silvi, D. L. Lauvergnat, P. C. Hiberty, Chem. Eur. J. 2005, 11, 6358.
9. H. Grützmacher, F. Breher, Angew. Chem. 2002, 114, 4178;
10. Angew. Chem. Int. Ed. 2002, 41, 4006, and references therein.
11. a) W. T. Borden in Enzyclopedia of Computational Chemistry (Ed.: P. von R. Schleyer), Wiley, New York, 1998, 708;
12. b) Biradicals (Ed.: W. T. Borden), Wiley, New York, 1982;
13. c) J. A. Berson, Acc. Chem. Res. 1997, 30, 238;
14. d) D. A. Dougherty, Acc. Chem. Res. 1991, 24, 88;
15. e) L. Salem, C. Rowland, Angew. Chem. 1972, 84, 86;
16. Angew. Chem. Int. Ed. Engl. 1972, 11,92;
17. f)W.T. Borden, H. Iwamura, J. A. Berson, Acc. Chem. Res. 1994, 27, 109;
18. g) A. Rajca, Chem. Rev. 1994, 94, 871.
19. a) P. von R. Schleyer, R. Janoschek, Angew. Chem. 1987, 99, 1312;
20. Angew. Chem. Int. Ed. Engl. 1987, 26, 1267.
21. b (with E = Si, Ge, Sn) denotes the distance between the bridgehead atoms in metalla-[1.1.1]propellanes.
22. W. W. Schoeller, T. Dabisch, T. Busch, Inorg. Chem. 1987, 26, 4383.
23. a) S. Nagase, Polyhedron 1991, 10, 1299;
24. see also b) S. Nagase, T. Kudo, Organometallics 1987, 6, 2456;
25. c) S. Nagase, T. Kudo, Organometallics 1988, 7, 2534.
26. M. S. Gordon, K. A. Nguyen, M. T. Carroll, Polyhedron 1991, 10, 1247.
27. b bcp's may also result from reversed order of the o(E E) and σ*(E E) orbitals, so that the latter becomes the HOMO for metallapropellanes with M = Si, Ge, and Sn; see reference [16b].
28. N. Gallego-Planas, M. A. Whitehead, J. Mol. Struct. (Theochem) 1992, 260, 419.
29. a) V. Bonačkć-Koutecký, J. Koutecký, J. Michl, Angew. Chem. 1987, 99, 216;
30. Angew. Chem. Int. Ed. Engl. 1987, 26, 170.
31. For the theoretical treatment of (multi)radical species, see b) J. Cullen, Chem. Phys. 1996, 202, 217;
32. c) T. Van Voorhis, M. Head-Gordon, J. Chem. Phys. 2000, 112, 5633;
33. d) T. Van Voorhis, M. Head- Gordon, J. Chem. Phys. 2002, 117, 9190;
34. e) A. D. Dutoi, Y. Jung, M. Head-Gordon, J. Phys. Chem. A 2004, 108, 10270;
35. f) A. Sodt, G. J. O. Beran, Y. Jung, B. Austin, M. Head-Gordon, J. Chem. Theory Comput. 2006, 2, 300;
36. g) Y. M. Rhee, M. Head-Gordon, J. Am. Chem. Soc. 2008, 130, 3878.
37. "A biradicaloid is a closed-shell species derived from a singlet biradical by a weak interaction between the radical centers" M. J. S. Dewar, E. F. Healy, Chem. Phys. Lett. 1987, 141, 521.
38. See, for example, a) K. A. Nguyen, M. T. Carroll, M. S. Gordon, J. Am. Chem. Soc. 1991, 113, 7924;
39. b) N. Sandstrom, H. Ottosson, Chem. Eur. J. 2005, 11, 5067;
40. c) Y. Wang, J. Ma, S. Inagaki, Tetrahedron Lett. 2005, 46, 5567;
41. d) A. Ebrahimi, F. Deyhimi, H. Roohi, J. Mol. Struct. (Theochem) 2003, 626, 223;
42. e) D. B. Kitchen, J. E. Jackson, L. C. Allen, J. Am. Chem. Soc. 1990, 112, 3408.
43. 6]: G. Fischer, V. Huch, P. Mayer, S. K. Vasisht, M. Veith, N. Wiberg, Angew. Chem. 2005, 117, 8096;
44. Angew. Chem. Int. Ed. 2005, 44, 7884;
45. 6]: A. Schnepf, R. Köppe, Angew. Chem. 2003, 115, 940;
46. Angew. Chem. Int. Ed. 2003, 42, 911;
47. 6]: A. Schnepf, C. Drost, Dalton Trans. 2005, 3277;
48. 6]: N. Wiberg, H.-W. Lerner, S. Wagner, H. Nöth, T. Seifert, Z. Naturforsch. B 1999, 877.
49. a) L. R. Sita, I. Kinoshita, J. Am. Chem. Soc. 1992, 114, 7024;
50. b) L. R. Sita, I. Kinoshita, J. Am. Chem. Soc. 1991, 113, 5070;
51. c) L. R. Sita, I. Kinoshita, J. Am. Chem. Soc. 1990, 112, 8839;
52. d) L. R. Sita, R. D. Bickerstatt Kinoshita, J. Am. C0hem. Soc. 1989, 111, 6454.
53. C. Drost, M. Hildebrand, P. Lönnecke, Main Group Met. Chem. 2002, 25, 93.
54. A. F. Richards, M. Brynda, P. P. Power, Organometallics 2004, 23, 4009.
55. 6](R = 2,4,6-tri(isopropyl)phenyl) formally represents a valence isomer of a pentasila[1.1.1]propellane showing only one ligand-free silicon cluster atom: D. Scheschkewitz, Angew. Chem. 20r05, 117, 3014;
56. 2]is also known: Y. Kabe, T. Kawase, J. Okada, O. Yamashita, M. Goto, S. Masamune, Angew. Chem. 1990, 102, 823;
57. Angew. Chem. Int. Ed. Engl. 1990, 29, 794.
58. 4] cluster for which a singlet biradicaloid resonance form was postulated: A. F.
59. Richards, M. Brynda, M. M. Olmstead, P. P. Power, Organo-metallics 2004, 23, 2841.
60. a) V. Y. Lee, A. A. Basova, I. A. Matchkarovskaya, V. I. Faustov,vM. P. Egorov, O. M. Nefedov, R. D. Rakhimov, K. P. Butin, J. Organomet. Chem. 1995, 499, 27;
61. b) A. Sekiguchi, T. Fukawa, M. Nakamoto, V. Ya. Lee, M. Ichinohe, J. Am. Chem. Soc. 2002, 124, 9865;
62. c) E. Rivard, J. Steiner, J. C. Fettinger, J. R. Giuliani, M. P. Augustine, P. P. Power, Chem. Commun. 2007, 4919.
63. 3}](D), which is an obvious result of the size difference of the cluster constituents.
64. Only some minor features of the experimental spectrum could not be reproduced by the simulation. The value for A ⊥ can only be given as an approximation owing to signal overlap and a relatively large line width.
65. It is important to note that the quantity of radical character is fundamentally different from the theory of radical behavior. Radical character serves as theoretical measure, whereas radical behavior is experimentally observed for such species. See reference [14] for more details.
66. 6] were not observed.
67. For the same radical-type reactivity of a 1,3-dibora-2,4-diphos- phoniocyclobutane-1,3-diyl see H. Amii, L. Vranicar, H. Gornitzka, D. Bourissou, G. Bertrand, J. Am. Chem. Soc. 2004, 126, 1344.