Conformational and isomeric preferences of six-membered inorganic heterocycles [EtNP(E)(OR)] 3 (E = lone pair, O, S, or Se): A Synthetic, spectroscopic, structural, and computational study

Inorganic Chemistry

Volumn 48, Issue 5, 2009, Pages 2048-2059

  Murugavel, Ramaswamy ^a   Prabusankar, Ganesan ^a   Sharma, Ashish ^a   Sunoj, Raghavan B ^a   Butcher, Ray J ^b  

^a INDIAN INSTITUTE OF TECHNOLOGY BOMBAY   (India)

^b HOWARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 64549148935     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic801945q     Document Type: Article

References (79)

1. For selected examples, see: (a) Witt, M.; Roesky, H. W. Chem. Rev. 1994, 94, 1163.
2. (b) Olivers, T. Chem. Rev. 1985, 85, 341.
3. (c) Chivers, T. Acc. Chen. Res. 1984, 17, 166.
4. (d) Chivers, T.; Hilts, R. W. Coor. Chem. Rev. 1994, 137, 201.
5. (e) Steiner, A.; Zacchini, S.; Richards, P. I. Coord. Chem. Rev. 2002, 227, 193.
6. (f) Bickley, J. F.; Copsey, M. C.; Jeffery, J. C.; Leedham, A. P.; Russell, C. A.; Stalke, D.; Steiner, A.; Stey, T.; Zacchini, S. J. Chem. Soc., Dalton Trans. 2004. 989.
7. (g) Baier, F.; Fei, Z.; Gomitzka, H.; Murso, A.; Neufeld, S.; Pfeiffer, M.; Rudenauer, I.; Steiner, A.; Stey, T.; Stalke, D. J. Organomet. Chem. 2002, 661, 111.
8. (h) Fleischer, R.; Stalke, D. Coord. Chem. Rev. 1998, 176, 431.
9. (i) Edelmann, F. T. Coord. Chem. Rev. 1994, 137, 403.
10. (j) Westerhausen, M. Coord. Chem. Rev. 1998, 176, 157.
11. (k) Beswick, M. A.; Wright, D. S. Coord. Chem. Rev. 1998, 176, 373.
12. (l) Balakrishna, M. S.; Eisler, D. J.; Chivers, T. Chem. Soc. Rev. 2007, 36, 350.
13. (m) Waggoner, K. M.; Hope, H.; Power, P. P. Angew. Chem., Int. Ed. Engl. 1988, 27, 1699.
14. (a) Harvey, D. A.; Keat, R.; Rycroft, D. S. J. Chem. Soc., Dalton Trans. 1983, 425.
15. (b) Keat, R. Top. Curr. Chem. 1982, 102, 89.
16. (c) Murugavel, R.; Krishnamurthy, S. S.; Chandrasekhar, J.; Nethaji, M. Inorg. Chem. 1993, 32, 5447.
17. (d) Thirupathi, N.; Krishnamurthy, S. S.; Chandrasekhar, J. Chem. Commun. 1996, 1703.
18. (a) Holmes, R. R. J. Am. Chem. Soc. 1960, 82, 5509.
19. (b) Zeiss, W.; Pointner, A.; Engelhardt, C.; Klehr, H. Z. Anorg. Allg. Chem. 1981, 475, 256.
20. (c) Galliano, K. D.; Paddock, N. L. Can. J. Chem. 1985, 63, 314.
21. (a) Niecke, E.; Nieger, M.; Reichert, F. Angew. Chem., Int. Ed. Engl. 1988, 27, 1715.
22. (b) Burford, N.; Cameron, T. S.; Conroy, K, D.; Ellis, B.; Lumsden, M.; Macdonald, C. L. B.; McDonald, R.; Phillips, A. D.; Ragogna, P. J.; Schurko, R. W.; Walsh, D.; Wasylishen, R. E. J. Am. Chem. Soc. 2002, 124, 14012.
23. (c) Burford, N.; Conroy, K. D.; Landry, J. C: Ragogna, P. J.; Ferguson, M. J.; McDonald. R. Inorg. Chem. 2004, 43, 8245.
24. Representative recent examples: (a) Chakravarty, M.; Suresh, R. R.; Swamy, K. C. K. Inorg. Chern. 2007, 46, 9819.
25. (b) Rastaetter, M.; Roesky, P. W.; Gudat, D.; Deacon, G. B.; Junk, P. C. Chem.-Eur. J. 2007, 13, 7410.
26. (c) Davidson, R. J.; Weigand, J. J.; Burford, N.; Cameron, T. S.; Decken, A.; Werner-Zwanziger, U. Chem. Commun. 2007, 4671.
27. (e) Gonzalez-Calera, S.; Eisler, D. J.; Morey, J. V.; McPartlin, M.; Singh, S.; Wright, D. S. Angew. Chem., Int. Ed. 2008, 47, 1111.
28. (f) Chan, W. T. K.; Eisler, D.; Garcia, F.; Gonzalez-Calera, S.; McPartlin, M.; Morey, J. V.; Mulvey, R. E.; Singh, S.; Steiner, A.; Wright, D. S. Chem. Commun. 2008, 2251.
29. (g) Besli, S.; Coles, S. J.; Davies, D. B.; Erkovan, A. O.; Hursthouse, M. B.; Kilic, A. Inorg. Chem. 2008, 47, 5042.
30. (h) Suresh, D.; Balakrishna, M. S.; Mague, J. T. Dalton Trans. 2008, 3272.
31. 3 with silanetriol, see: Murugavel, R.; Prabusankar, G.; Walawalkar, M. G. Inorg. Chem. 2001, 40, 1084.
32. (a) Murugavel, R.; Chandrasekhar, V.; Voigt, A.; Roesky, H. W.; Schmidt, H.-G.; Noltemeyer, M. Organometallics 1995, 14, 5298.
33. (b) Murugavel, R.; Chandrasekhar, V.; Roesky, H. W. Acc. Chem. Res. 1996, 29, 183.
34. (c) Murugavel, R.; Voigt, A.; Walawalkar, M. G.; Roesky, H. W. Chem. Rev. 1996, 96, 2205.
35. Thomas, L. C. Interpretation of Infrared Spectra of Organo-Phosphorus Compounds; Heyden and Son Ltd.; Chichester, U. K., 1974.
36. (a) Lickiss, P. D. Adv. Inorg. Chem. 1995, 42, 147.
37. (b) Chandrasekhar, V.; Boomishankar, R.; Nagendran, S. Chem. Rev. 2004, 104, 5847.
38. (c) Murugavel, R.; Böttcher, P.; Voigt, A.; Walawalkar, M. G.; Roesky, H. W.; Teichert, M.; Noltemeyer, M. Chem. Commun. 1996, 2417.
39. (a) Gouzyr, A. I.; Wessel, H.; Barnes, C. E.; Roesky, H. W.; Teichert, M.; Usón, I. Inorg. Chem. 1997, 36, 3392.
40. (b) Voigt, A.; Walawalkar, M. G.; Murugavel, R.; Roesky, H. W.; Parisini, E.; Lubini, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 2203.
41. (c) Lickiss, P. D.; Litster, S. A.; Redhouse, A. D.; Wisener, C. A. J. Chem, Soc., Chem. Commun. 1991, 173.
42. (a) Walawalkar, M. G.; Roesky, H. W.; Muragavel, R. Acc. Chem. Res. 1999, 32, 117.
43. (b) Murugavel, R.; Walawalkar, M. G.; Pothiraja, R.; Rao, C. N. R.; Choudhury, A. Chem. Rev. 2008, 108, 3549.
44. Thirupathi, N.; Krishnamurthy, S. S.; Nethaji, M. Phosphorus, Sulfur, Silicon 1997, 123, 263.
45. (a) Thirupathi, N.; Krishnamurthy, S. S.; Nethaji, M. Inorg. Chem. 1999, 38, 1093.
46. (a) Cruickshank, D. W. J. Acta Crystallogr. 1964, 17, 671.
47. (b) Elias, A. J.; Teamley, B.; Haist, R.; Oberhammer, H.; Henkel, G.; Krebs, B.; Lork, E.; Mews, R.; Shreeve, J. M. J. Am. Chem. Soc. 2001, 123, 10299.
48. Cruickshank, D. W. J. J. Chem. Soc. 1961, 5486.
49. (a) Necas, M.; Foreman, M. R. S. J.; Marek, J.; Woollins, J. D.; Novosad, J. Nrw J. Chem. 2001, 25, 1256.
50. (b) Cupertino, D.; Keyte, R.; Slawin, A. M. Z.; Williams, D. J.; Woollins, J. D. Inorg. Chem. 1996, 35, 2695.
51. Corbridge, D. E. C. The Structural Chemistry of Phosphorus; Elsevier: Amsterdam, 1974.
52. (a) Olthof, R.; Migchelsen, T.; Vos, A. Acta Crystallogr. 1965, 19, 596.
53. (b) Ansell, G. B.; Bullen, G. J. J. Chem. Soc. A 1968, 3026.
54. (c) Johnson, O.; Murray, M.; Woodward, G. J. Chem. Soc., Dalton Trans. 1989, 821.
55. (d) Karthikeyan, S.; Vyas, K.; Krishnamurthy, S. S.; Cameron, T. S.; Vincent, B. R. J. Chem. Soc., Dalton Trans. 1988, 1371.
56. Zeiss, W.; Klehr, H. Z. Naturforsch. 1980, 35B, 1179.
57. Murugavel, R.; Thirupathi, N.; Krishnamurthy, S. S.; Nethaji, M. Heteroatom Chem. 1995, 6, 63.
58. (a) Parvez, M.; Kwon, S.; Allcock, H. R. Acta Crystallogr, Sect. C 1991, C47, 466.
59. (b) Steinberger, H. U.; Ziemer, B.; Meisel, M. Acta Crystallogr., Sect. C 2001, C57, 323.
60. (c) Steinberger, H. U.; Ziemer, B.; Meisel, M. Acta Crystallogr., Sect. C 2001, C57, 835.
61. (d) Steinberger, H. U.; Ziemer, B.; Meisel, M. Acta Crystallogr. 1979, B35, 1261.
62. (e) Bhattacharyya, P.; Slawin, A. M. Z.; Woollins, J. D. J. Organomet. Chem. 2001. 623, 116.
63. (f) Sekar, P.; Ibers, J. A. Inorg. Chem. 2003, 42, 6294.
64. Full details of the degree of pyramidalization (calculated as the difference between a fully planar situation (angle = 360°) and the sum of angles around the nitrogen atom) along with other structural parameters are summarized in the Supporting Information.
65. Reed, A. E.; Schleyer, P. v. R. J. Am. Chem. Soc. 1990, 112, 1434.
66. Analyses of charge distribution using the natural population analyses exhibited fairly high charges on phosphorus, which ranges from +1.89 to +1.92 with the P-S systems, while the variation is found to be somewhat less pronounced with the P-Se systems, having variations from +1.82 to +1.84. In all of these molecules, 3d orbital contribution towards bonding was found to be only about 0.09, as revealed by the natural electronic contribution. This implies that the d orbital is mainly acting as a polarization function, and it is playing only a secondary role in bonding. In both cases, phosphorus was found to have four highly polarized σ natural bond orbitals.
67. See Supporting Informationfor a detailed list of NBO delocaliza-tions.
68. Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory Chemicals, 3rd ed.; Pergamon Press: London, 1988,
69. (a) Gemmill, J.; Keat, R.; Hani, R.; Neilson, R. H. Inorg. Synth. 1988, 25, 13.
70. (b) Nixon, J. F. J. Chem. Soc. A 1968, 2689.
71. WinGX. version 1.64.05: Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837.
72. Altomare, A.; Cascarano, G.; Giacovazzo, C.; Gualardi, A. J. Appl. Crystallogr. 1993. 26, 343.
73. Sheldrick, G. M. SHELXL-97; University of Göttingen, Göttingen, Germany, 1997.
74. Frisch, M. J.; Tracks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.11.4;Gaussian, Inc.: Pittsburgh, PA, 1998.
75. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
76. (b) Becke, A. D. Phys. Rev. A: At., Mol., Opt. Phys. 1998, 38, 3098.
77. (c) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B: Condens. Matter Mater. Phys. 1998, 37, 785.
78. (a) Glendening, E. D.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. NBO, version 3.1.
79. (b) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899.