peri-Interactions in naphthalenes, 3 [1]. On hypercoordination in 8-Dimethylamino-naphth-1-yl-phosphonium salts and -phosphines

Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences

Volumn 55, Issue 1, 2000, Pages 12-20

  Schiemenz, Günter Paulus ^a   Bukowski, Ralph ^a   Eckholtz, Lars ^a   Varnskühler, Bernhard ^a  

^a UNIVERSITY OF KIEL   (Germany)

Author keywords

1H NMR Data; 31P NMR Data; Interatomic Distances; Naphthalenes; Repulsive Interaction

Indexed keywords

PHOSPHORUS COMPOUNDS; SALTS;

31P-NMR; EXPERIMENTAL EVIDENCE; HYPERCOORDINATION; INTER-ATOMIC DISTANCES; NMR DATA; PHOSPHONIUM SALTS; REPULSIVE INTERACTIONS;

NAPHTHALENE;

EID: 0040141837     PISSN: 09320776     EISSN: None     Source Type: Journal    
DOI: 10.1515/znb-2000-0104     Document Type: Article

References (80)

1. 2nd communication: G. P. Schiemenz, Posphorus Sulfur and Silicon, in press.
2. For a seminal paper, see W. B. Schweizer, G. Procter, M. Kaftory, J. D. Dunitz, Helv. Chim. Acta 61, 2783 (1978).
3. Cf., e. g., T. Herbst, G. P. Schiemenz, C. Wolff, Magn. Res. Chem. 26, 608 (1988); T. Herbst, G. P. Schiemenz, Z. Naturforsch. 44b, 866 (1989).
4. Cf., e. g., T. Herbst, G. P. Schiemenz, C. Wolff, Magn. Res. Chem. 26, 608 (1988); T. Herbst, G. P. Schiemenz, Z. Naturforsch. 44b, 866 (1989).
5. N. F. Hall, M. R. Sprinkle, J. Am. Chem. Soc. 54, 3469 (1932); H. A. Staab, Einführung in die theoretische organische Chemie, pp. 631, 637, Verlag Chemie, Weinheim (1959).
6. N. F. Hall, M. R. Sprinkle, J. Am. Chem. Soc. 54, 3469 (1932); H. A. Staab, Einführung in die theoretische organische Chemie, pp. 631, 637, Verlag Chemie, Weinheim (1959).
7. E. g. C. Brelière, F. Carré, R. J. P. Corriu, G. Royo, M. Wong Chi Man, J. Lapasset, Organometallics 13, 307 (1994); C. Chuit, R. J. P. Corriu, C. Reye, J. C. Young, Chem. Rev. 93, 1371 (1993), and references therein.
8. E. g. C. Brelière, F. Carré, R. J. P. Corriu, G. Royo, M. Wong Chi Man, J. Lapasset, Organometallics 13, 307 (1994); C. Chuit, R. J. P. Corriu, C. Reye, J. C. Young, Chem. Rev. 93, 1371 (1993), and references therein.
9. + substructure, is not known. In the first case, it would be irrelevant to the question of hypercoordination at pseudo-tetracoordinate (i. e. phosphine) phosphorus, in the second case, to the question of pseudo-heptacoordination, and in the third case, to both.
10. + substructure, is not known. In the first case, it would be irrelevant to the question of hypercoordination at pseudo-tetracoordinate (i. e. phosphine) phosphorus, in the second case, to the question of pseudo-heptacoordination, and in the third case, to both.
11. M. Chauhan, C. Chuit, R. J. P. Corriu, C. Reyé, J.-P. Declercq, A. Dubourg, J. Organomet. Chem. 510, 173 (1996).
12. C. Chuit, R. J. P. Corriu, P. Monforte, C. Reyé, J.-P. Declercq, A. Dubourg, J. Organomet. Chem. 511, 171 (1996).
13. -1 for 5b] is incompatible with the conclusion of weak interactions between N and P in 5b [7] and 5c (Eur. J. Inorg. Chem., loc. cit., p. 1852) derived from the N-P distances.
14. -1 for 5b] is incompatible with the conclusion of weak interactions between N and P in 5b [7] and 5c (Eur. J. Inorg. Chem., loc. cit., p. 1852) derived from the N-P distances.
15. -1 for 5b] is incompatible with the conclusion of weak interactions between N and P in 5b [7] and 5c (Eur. J. Inorg. Chem., loc. cit., p. 1852) derived from the N-P distances.
16. G. P. Schiemenz, B. Schiemenz, S. Petersen, C. Wolff, Chirality 10, 180 (1998).
17. G. P. Schiemenz, Chem. Listy 92, 269 (1998).
18. cov, has been devised; cf., e. g., R. O. Day, T. K. Prakasha, R. R. Holmes, H. Eckert, Organometallics 13, 1285 (1994), p. 1290; T. K. Prakasha, S. Srinivasan, A. Chandrasekaran, R. O. Day, R. R. Holmes, J. Am. Chem. Soc. 117, 10003 (1995), p. 10006. We find it hard to reconcile this concept with the experimental experience that bond lengths tend to be strongly resistant to stretching. Forced to increased interatomic distances of even much less than 250 pm, any two-electron bond will break rather than stretch ad libitum (cf. G. Kaupp, J. Boy, Angew. Chem. 109, 48 (1997); Angew. Chem. Int. Ed. Engl. 36, 48 (1997)).
19. cov, has been devised; cf., e. g., R. O. Day, T. K. Prakasha, R. R. Holmes, H. Eckert, Organometallics 13, 1285 (1994), p. 1290; T. K. Prakasha, S. Srinivasan, A. Chandrasekaran, R. O. Day, R. R. Holmes, J. Am. Chem. Soc. 117, 10003 (1995), p. 10006. We find it hard to reconcile this concept with the experimental experience that bond lengths tend to be strongly resistant to stretching. Forced to increased interatomic distances of even much less than 250 pm, any two-electron bond will break rather than stretch ad libitum (cf. G. Kaupp, J. Boy, Angew. Chem. 109, 48 (1997); Angew. Chem. Int. Ed. Engl. 36, 48 (1997)).
20. cov, has been devised; cf., e. g., R. O. Day, T. K. Prakasha, R. R. Holmes, H. Eckert, Organometallics 13, 1285 (1994), p. 1290; T. K. Prakasha, S. Srinivasan, A. Chandrasekaran, R. O. Day, R. R. Holmes, J. Am. Chem. Soc. 117, 10003 (1995), p. 10006. We find it hard to reconcile this concept with the experimental experience that bond lengths tend to be strongly resistant to stretching. Forced to increased interatomic distances of even much less than 250 pm, any two-electron bond will break rather than stretch ad libitum (cf. G. Kaupp, J. Boy, Angew. Chem. 109, 48 (1997); Angew. Chem. Int. Ed. Engl. 36, 48 (1997)).
21. cov, has been devised; cf., e. g., R. O. Day, T. K. Prakasha, R. R. Holmes, H. Eckert, Organometallics 13, 1285 (1994), p. 1290; T. K. Prakasha, S. Srinivasan, A. Chandrasekaran, R. O. Day, R. R. Holmes, J. Am. Chem. Soc. 117, 10003 (1995), p. 10006. We find it hard to reconcile this concept with the experimental experience that bond lengths tend to be strongly resistant to stretching. Forced to increased interatomic distances of even much less than 250 pm, any two-electron bond will break rather than stretch ad libitum (cf. G. Kaupp, J. Boy, Angew. Chem. 109, 48 (1997); Angew. Chem. Int. Ed. Engl. 36, 48 (1997)).
22. -, there is no dichotomy of "normal" and "hypercoordinate" bonds.
23. Note that naphthostyril and naphthosultam are easily formed: A. G. Eckstrand, J. Prakt. Chem. N. F. 38, 139 (1888); F. Dannerth, J. Am. Chem. Soc. 29, 1319 (1907).
24. Note that naphthostyril and naphthosultam are easily formed: A. G. Eckstrand, J. Prakt. Chem. N. F. 38, 139 (1888); F. Dannerth, J. Am. Chem. Soc. 29, 1319 (1907).
25. Note that the tetraphenylphosphonium cation reacts with phenyllithium to give pentaphenylphosphorane (G. Wittig, M. Rieber, Liebigs Ann. Chem. 562, 187 (1949)) whereas triphenylphosphine does not behave as an electrophile towards organolithium reagents.
26. G. P. Schiemenz, E. Papageorgiou, Phosphorus Sulfur 13, 41 (1982).
27. In loc. cit. [8], the discussion of our paper [16] is confined to the statement that "the, possible existence of intramolecular N→P interactions in these compounds has rarely been considered", and to the melting points of 3aI, 5a and the phosphine sulfide of 5a. Cf. loc. cit. [6, 7, 9].
28. Schiemenz, Papageorgiou [16], Table I, entry 7.
29. J. B. Hendrickson, M. L. Maddox, J. J. Sims, H. D. Kaesz, Tetrahedron 20, 449 (1964).
30. Schiemenz, Papageorgiou [16], Table I, entry 6.
31. 2, 60 MHz) (Schiemenz, Papageorgiou [16], Table I, entry 74).
32. Note that F. Carré, M. Chauhan, C. Chuit, R. J. P. Corriu, C. Reyé, Phosphorus, Sulfur and Silicon 123, 181 (1997), p. 188, quoted this value as δ of the ethyl ester.
33. For examples, cf. Schiemenz, Papageorgiou [16], Table I, entries 58, 59, 62, 63, 72, 73.
34. G. P. Schiemenz, J. Mol. Structure 16, 99 (1973).
35. Schiemenz, Papageorgiou [16], Table I, entry 173.
36. Schiemenz, Papageorgiou [16], Table I, entry 171.
37. Cf., e. g., Schiemenz, Papageorgiou [16], Table II.
38. Schiemenz, Papageorgiou [16], Table I, entry 1.
39. Schiemenz, Papageorgiou [16], Table I, entry 2.
40. S. Petersen, Ph. D. thesis, University of Kiel (1998).
41. 3 groups in 5c (cf. Chuit et al. [6]) can be ascribed to hindered rotation due to sterical hindrance and is, then, no evidence for dative N→P interaction.
42. 10 skeleton and, hence, to increased "aromatic shielding".
43. 31 Nuclear Magnetic Resonance (Topics in Phosphorus Chemistry 5(1967)), 381-383, 385.
44. +-C(1)-C(2) and F-C(2)-C(1) = 120°.
45. +-C(1)-C(2) and F-C(2)-C(1) = 120°.
46. +-C(1)-C(2) and F-C(2)-C(1) = 120°.
47. S. S. Batsanov, Izvest. Akad. Nauk, Ser. Khim. 24 (1995); Russian Chemical Bulletin 44, 18 (1995). Corriu et al. [6 - 8] used the figures of A. Bondi, J. Phys. Chem. 68. 441 (1964), N: 155, P: 180 pm.
48. S. S. Batsanov, Izvest. Akad. Nauk, Ser. Khim. 24 (1995); Russian Chemical Bulletin 44, 18 (1995). Corriu et al. [6 - 8] used the figures of A. Bondi, J. Phys. Chem. 68. 441 (1964), N: 155, P: 180 pm.
49. S. S. Batsanov, Izvest. Akad. Nauk, Ser. Khim. 24 (1995); Russian Chemical Bulletin 44, 18 (1995). Corriu et al. [6 - 8] used the figures of A. Bondi, J. Phys. Chem. 68. 441 (1964), N: 155, P: 180 pm.
50. Cf. S. S. Batsanov, J. Chem. Soc., Dalton Trans., 1541 (1998).
51. L. Pauling, The Nature of the Chemical Bond and the Structure of Molecules and Crystals. An Introduction to Modern Structural Chemistry, p. 168, Cornell University Press, Ithaca, NY (1945).
52. 4 is tetracoordinate. According to Holmes' procedure [12], the tetrahedral character (in analogy to Holmes' TBP and octahedral characters) of hydrogen in methane is 63%.
53. Pauling [37], p. 167.
54. vdW" in the terms of the advocates of hypercoordination).
55. 4 system performed by the authors naturally have no bearing on the deformation of peri-substituted naphthalenes.
56. 4 system performed by the authors naturally have no bearing on the deformation of peri-substituted naphthalenes.
57. 4 system performed by the authors naturally have no bearing on the deformation of peri-substituted naphthalenes.
58. Staab [4], pp. 200-201.
59. H. W. W. Ehrlich, Acta Crystallogr. 10, 699 (1957).
60. E. g., 1,8-dimethyl-naphthalene: D. Bright, I. E. Maxwell, J. de Boer, J. Chem. Soc., Perkin Trans. II, 2101 (1973); 1,8-diphenyl-naphthalene: R. L. Clough, W. J. Kung, R. E. Marsh, J. D. Roberts, J. Org. Chem. 41, 3603 (1976); 1,8-dimethoxy-naphthalene: L. J. Fitzgerald, J. C. Gallucci, R. E. Gerkin, Acta Crystallogr. B 47, 776 (1991).
61. E. g., 1,8-dimethyl-naphthalene: D. Bright, I. E. Maxwell, J. de Boer, J. Chem. Soc., Perkin Trans. II, 2101 (1973); 1,8-diphenyl-naphthalene: R. L. Clough, W. J. Kung, R. E. Marsh, J. D. Roberts, J. Org. Chem. 41, 3603 (1976); 1,8-dimethoxy-naphthalene: L. J. Fitzgerald, J. C. Gallucci, R. E. Gerkin, Acta Crystallogr. B 47, 776 (1991).
62. E. g., 1,8-dimethyl-naphthalene: D. Bright, I. E. Maxwell, J. de Boer, J. Chem. Soc., Perkin Trans. II, 2101 (1973); 1,8-diphenyl-naphthalene: R. L. Clough, W. J. Kung, R. E. Marsh, J. D. Roberts, J. Org. Chem. 41, 3603 (1976); 1,8-dimethoxy-naphthalene: L. J. Fitzgerald, J. C. Gallucci, R. E. Gerkin, Acta Crystallogr. B 47, 776 (1991).
63. Hydrogen bonds between peri substituents represent a special case which we intend to deal with elsewhere.
64. Note that (4-dimethylamino-phenyl)di(phenyl)-phosphine is first protonated at N: G. P. Schiemenz, Tetrahedron 27, 3231 (1971).
65. Data obtained from Chuit et al. [8], Table 4.
66. Data obtained from Chauhan et al. [7], Table 7. For the hydrobromide of 5c, the pertinent data have not been published [6].
67. 6.3° (average) in the hydrobromide of 5c (data obtained from the supplementary material of loc. cit. [6]).
68. cov(F-F) = 144 pm; cf. Staab [4], p. 193)). For similar phenomena, cf. F. Riedmiller, A. Jockisch, H. Schmidbaur, Organometallics 17, 4444 (1998), for a more detailed analysis of the force vectors operating in pen-substituted naphthalenes, Clough et al. [44].
69. cov(F-F) = 144 pm; cf. Staab [4], p. 193)). For similar phenomena, cf. F. Riedmiller, A. Jockisch, H. Schmidbaur, Organometallics 17, 4444 (1998), for a more detailed analysis of the force vectors operating in pen-substituted naphthalenes, Clough et al. [44].
70. cov(F-F) = 144 pm; cf. Staab [4], p. 193)). For similar phenomena, cf. F. Riedmiller, A. Jockisch, H. Schmidbaur, Organometallics 17, 4444 (1998), for a more detailed analysis of the force vectors operating in pen-substituted naphthalenes, Clough et al. [44].
71. Obtained from the data in loc. cit. [8], Table 4 (cf. ibid., p. 172: "no more than 2°" for "N-C(8)-P...C(1)").
72. Obtained from the data in loc. cit. [7], Table 7 (cf. ibid., p. 174: "the dihedral angle C13-P...N2-C21 of 27(1)°" [C13 = C(1), C21 = C(8), N2 = N of the more deformed DAN group]).
73. Obtained from loc. cit. [7], Table 8.
74. F. Carré, C. Chuit, R. J. P. Corriu, P. Monforte, N. K. Nayyar, C. Reyé, J. Organomet. Chem. 499, 147 (1995).
75. F. Carré, R. J. P. Corriu, A. Kpoton, M. Poirier, G. Royo, J. C. Young, C. Belin, J. Organomet. Chem. 470, 43 (1994). The averages of the pertinent data of different conformers have been used.
76. V. Pestunovich, S. Kirpichenko, M. Voronkov, in Z. Rappoport, Y. Apeloig (eds): The chemistry of organic silicon compounds, 2, John Wiley & Sons, Chichester, New York, Weinheim, Brisbane, Singapore, Toronto (1998), pp. 1447-1537 (average of 38 entries in Table 1 ranging from 196.5 to 224.0 pm).
77. 2, X = H, F, recently published by N. W. Mitzel, C. Kiener, D. W. H. Rankin, Organometallics 18, 3437 (1999).
78. A. Michaelis, H. v. Soden, Liebigs Ann. Chem. 229, 295 (1885).
79. G. Wittig, W. Haag, Chem. Ber. 88, 1654 (1955).
80. L. Horner, G. Simons, Phosphorus Sulfur 14, 189 (1983).