Heterocyclic systems containing tin(IV) - XIII [1]. Possible ceasing or inversion of the structural trans influence during the course of a bimolecular nucleophilic attack of a donor group in a series of SnIV rings

Polyhedron

Volumn 16, Issue 23, 1997, Pages 4005-4015

  Beuter, Mike ^a   Kolb, Ute ^a   Zickgraf, Andrea ^a   Bräu, Elmar ^a   Bletz, Michael ^a   Dräger, Martin ^a  

^a JOHANNES GUTENBERG UNIVERSITY   (Germany)

Author keywords

Bimolecular nucleophilic attack; Frontier orbitals; Germanium; Structural trans influence; Tin

Indexed keywords

EID: 0000807387     PISSN: 02775387     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0277-5387(97)00180-0     Document Type: Article

References (38)

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8. (a) March, J., Advanced Organic Chemistry, Reactions, Mechanisms, and Structure, p. 339, 4th edn., Wiley, New York (1992): "A large amount of work has been done on this subject. Though a great deal is known, much is poorly understood, and many results are anomalous and hard to explain";
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13. Musher, J. I., Angew. Chem., 1969, 81, 68; Angew. Chem. Int. Ed. Engl., 1969, 8, 54.
14. z)].
15. The assumption of a low-lying LUMO of pentacoordination is in accord with the experimental fact that a nucleophilic attack at a pentacoordinated Si atom is faster than an attack at a tetracoordinated Si atom: Chuit, C., Corriu, R. J. P., Reye, C. and Young, J. C., Chem. Rev., 1993, 93, 1371.
16. Kolb, U., Dräger, M., Dargatz, M. and Jurkschat, K., Organometallics, 1995, 14, 2827.
17. The compound 2 with R = F has an increased coordination at tin. The same holds for an analogous series of compounds with the donor C=O at tin in ref. [10].
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19. (a) Jurkschat, K. and Tzschach, A., J. Organomet. Chem., 1984, 272, C13;
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21. (c) For the diGrignard reagents see: Blomberg, C., Schat, G., Grootveld, H. H., Vreugdendhil, A. D. and Bickelhaupt, F., Liebigs Ann. Chem., 1972, 763, 148.
22. 4 [13].
23. Bräu, E., Falke, R., Ellner, A., Beuter, M., Kolb, U. and Dräger, M., Polyhedron, 1994, 13, 365.
24. 2) such a disorder could be resolved: Kolb, U. and Dräger, M., unpublished structure determinations.
25. 2: Rivière-Baudet, M., Morère, A., Britten, J. P. and Onyszchuk, M., J. Organomet. Chem., 1992, 423, C5. d(Ge - Cl) = 2.14 Å according to a chemically reasonable average of distances in 12 compounds: Cambridge Crystallographic Data Base, 10/1995.
26. Pauling, L. The Nature of the Chemical Bond, 3rd edn., Ch. 7, Cornell University Press, Ithaca, New York (1960).
27. (a) Harris, R. K., Kennedy, J. D. and McFarlane, W., In NMR and the Periodic Table, p. 309, Eds Harris, R. K. and Mann, B. E., Academic Press, London, New York, San Francisco (1978);
28. (b) Wrackmeyer, B., Annu. Rep. NMR Spectrosc., 1985, 16, 73.
29. Smith, P. J. and Tupciauskas, A. P., Annu. Rev. NMR Spectrosc., 1978, 8, 291.
30. 2).
31. Macharashvili, A. A., Shklover, V. E., Struchkov, Yu. T., Oleneva, G. I., Kramarova, E. P., Shipov, A. G. and Baukov, Yu. I., J. Chem. Soc., Chem. Commun., 1988, 683. The ceasing of the overall trans influence in the central part of the series is not mentioned explicitly in the paper.
32. (a) Program CACAO (Computer Aided Composition of Atomic Orbitals): Mealli, C. and Proserpio, D. M., J. Chem. Educ., 1990, 67, 399.
33. (b) Program HYPERCHEM: Hyperchem. Inc., 419 Philip Street, Waterloo, Ontario, Canada (1994).
34. ii (eV)/exponent: C(2s-21.40/1.625, 2p -11.40/1.625); H(1s -13.60/1.300); Cl(3s -26.30/2.183, 3p -14.20/1.733); Ge(4s -16.00/2.160, 4p -9.00/1.850); N(2s -26.00/1.950, 2p -13.40/1.950). Compilation by: Alvarez, S., Tables of Parameters for Extended Hückel Calculations, Barcelona, 1985.
35. Harris, R. K., Nuclear Magnetic Resonance Spectroscopy, A Physicochemical View, Pitman Books Ltd, London (1983).
36. n (n = 0-4; M = Si, Sn, Pb): Charissé, M., Mathiasch, B., Dräger, M. and Russo, U., Polyhedron, 1995, 14, 2429.
37. 2: + 122.0/-11.5/-65.9 ppm.
38. 0° perfect tetrahedron, 90° perfect trigonal bipyramid [10].