The PI+4 cation has an extremely large negative 31P nuclear magnetic resonance chemical shift, due to spin-orbit coupling: A quantum-chemical prediction and its confirmation by solid-state nuclear magnetic resonance spectroscopy

Journal of Chemical Physics

Volumn 110, Issue 8, 1999, Pages 3897-3902

  Kaupp, Martin ^a   Aubauer, Christoph ^b   Engelhardt, Günter ^c   Klapötke, Thomas M ^a   Malkina, Olga L ^d  

^a MAX PLANCK INSTITUT FÜR FESTKÖRPERFORSCHUNG   (Germany)

^b UNIVERSITY OF MUNICH   (Germany)

^c UNIVERSITY OF STUTTGART   (Germany)

^d INSTITUTE OF CHEMISTRY   (Slovakia)

Author keywords

[No Author keywords available]

Indexed keywords

APPROXIMATION THEORY; CHEMICAL BONDS; COMPUTER SIMULATION; ELECTRONS; MOLECULAR DYNAMICS; MOLECULAR STRUCTURE; OPTIMIZATION; PHOSPHORUS COMPOUNDS; POSITIVE IONS; PROBABILITY DENSITY FUNCTION; QUANTUM THEORY; SYNTHESIS (CHEMICAL);

FERMI CONTACT MECHANISM; INTERMOLECULAR INTERACTION; QUANTUM CHEMICAL CALCULATION; SPIN ORBIT COUPLING; TETRAHALOPHOSPHONIUM;

NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY;

EID: 0033593745     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.478243     Document Type: Article

References (58)

1. I. Morishima, K. Endo, and T. Yonezawa, J. Chem. Phys. 59, 3356 (1973); A. A. Cheremisin and P. V. Schastnev, J. Magn. Reson. 40, 459 (1980); P. Pyykkö, A. Görling, and N. Rösch, Mol. Phys. 61, 195 (1987).
2. I. Morishima, K. Endo, and T. Yonezawa, J. Chem. Phys. 59, 3356 (1973); A. A. Cheremisin and P. V. Schastnev, J. Magn. Reson. 40, 459 (1980); P. Pyykkö, A. Görling, and N. Rösch, Mol. Phys. 61, 195 (1987).
3. I. Morishima, K. Endo, and T. Yonezawa, J. Chem. Phys. 59, 3356 (1973); A. A. Cheremisin and P. V. Schastnev, J. Magn. Reson. 40, 459 (1980); P. Pyykkö, A. Görling, and N. Rösch, Mol. Phys. 61, 195 (1987).
4. R. G. Kidd, Annu. Rep. NMR Spectrosc. 10A, 2 (1980); 23, 85 (1991).
5. R. G. Kidd, Annu. Rep. NMR Spectrosc. 10A, 2 (1980); 23, 85 (1991).
6. Multinuclear NMR, edited by J. Mason (Plenum, New York, 1987).
7. See, e.g., H. Nakatsuji, H. Takashima, and M. Hada, Chem. Phys. Lett. 233, 95 (1995); H. Takashima, M. Hada, and H. Nakatsuji, ibid. 235, 13 (1995); H. Nakatsuji, T. Nakajima, M. Hada, H. Takashima, and S. Tanaka, ibid. 247, 418 (1995); H. Nakatsuji, M. Hada, T. Tejima, T. Nakajima, and M. Sugimoto, ibid. 249, 284 (1996); C. C. Ballard, M. Hada, H. Kaneko, and H. Nakatsuji, ibid. 254, 170 (1996); H. Kaneko, M. Hada, T. Nakajima, and H. Nakatsuji, ibid. 261, 1 (1996).
8. See, e.g., H. Nakatsuji, H. Takashima, and M. Hada, Chem. Phys. Lett. 233, 95 (1995); H. Takashima, M. Hada, and H. Nakatsuji, ibid. 235, 13 (1995); H. Nakatsuji, T. Nakajima, M. Hada, H. Takashima, and S. Tanaka, ibid. 247, 418 (1995); H. Nakatsuji, M. Hada, T. Tejima, T. Nakajima, and M. Sugimoto, ibid. 249, 284 (1996); C. C. Ballard, M. Hada, H. Kaneko, and H. Nakatsuji, ibid. 254, 170 (1996); H. Kaneko, M. Hada, T. Nakajima, and H. Nakatsuji, ibid. 261, 1 (1996).
9. See, e.g., H. Nakatsuji, H. Takashima, and M. Hada, Chem. Phys. Lett. 233, 95 (1995); H. Takashima, M. Hada, and H. Nakatsuji, ibid. 235, 13 (1995); H. Nakatsuji, T. Nakajima, M. Hada, H. Takashima, and S. Tanaka, ibid. 247, 418 (1995); H. Nakatsuji, M. Hada, T. Tejima, T. Nakajima, and M. Sugimoto, ibid. 249, 284 (1996); C. C. Ballard, M. Hada, H. Kaneko, and H. Nakatsuji, ibid. 254, 170 (1996); H. Kaneko, M. Hada, T. Nakajima, and H. Nakatsuji, ibid. 261, 1 (1996).
10. See, e.g., H. Nakatsuji, H. Takashima, and M. Hada, Chem. Phys. Lett. 233, 95 (1995); H. Takashima, M. Hada, and H. Nakatsuji, ibid. 235, 13 (1995); H. Nakatsuji, T. Nakajima, M. Hada, H. Takashima, and S. Tanaka, ibid. 247, 418 (1995); H. Nakatsuji, M. Hada, T. Tejima, T. Nakajima, and M. Sugimoto, ibid. 249, 284 (1996); C. C. Ballard, M. Hada, H. Kaneko, and H. Nakatsuji, ibid. 254, 170 (1996); H. Kaneko, M. Hada, T. Nakajima, and H. Nakatsuji, ibid. 261, 1 (1996).
11. See, e.g., H. Nakatsuji, H. Takashima, and M. Hada, Chem. Phys. Lett. 233, 95 (1995); H. Takashima, M. Hada, and H. Nakatsuji, ibid. 235, 13 (1995); H. Nakatsuji, T. Nakajima, M. Hada, H. Takashima, and S. Tanaka, ibid. 247, 418 (1995); H. Nakatsuji, M. Hada, T. Tejima, T. Nakajima, and M. Sugimoto, ibid. 249, 284 (1996); C. C. Ballard, M. Hada, H. Kaneko, and H. Nakatsuji, ibid. 254, 170 (1996); H. Kaneko, M. Hada, T. Nakajima, and H. Nakatsuji, ibid. 261, 1 (1996).
12. See, e.g., H. Nakatsuji, H. Takashima, and M. Hada, Chem. Phys. Lett. 233, 95 (1995); H. Takashima, M. Hada, and H. Nakatsuji, ibid. 235, 13 (1995); H. Nakatsuji, T. Nakajima, M. Hada, H. Takashima, and S. Tanaka, ibid. 247, 418 (1995); H. Nakatsuji, M. Hada, T. Tejima, T. Nakajima, and M. Sugimoto, ibid. 249, 284 (1996); C. C. Ballard, M. Hada, H. Kaneko, and H. Nakatsuji, ibid. 254, 170 (1996); H. Kaneko, M. Hada, T. Nakajima, and H. Nakatsuji, ibid. 261, 1 (1996).
13. V. G. Malkin, O. L. Malkina, L. A. Eriksson, and D. R. Salahub, in Modern Density Functional Theory: A Tool for Chemistry, edited by J. M. Seminario and P. Politzer (Elsevier, Amsterdam, 1995), Vol. 2.
14. V. G. Malkin, O. L. Malkina, and D. R. Salaub, Chem. Phys. Lett. 261, 335 (1996).
15. M. Kaupp, O. L. Malkina, and V. G. Malkin, Chem. Phys. Lett. 265, 55 (1996).
16. M. Kaupp, O. L. Malkina, V. G. Malkin, and P. Pyykkö, Chem.-Eur. J. 4, 118 (1998).
17. M. Bühl, M. Kaupp, O. L. Malkina, V. G. Malkin, J. Comp. Chem. 20, 91 (1999).
18. Our preliminary investigations indicate that the NHD found for late transition metals is only in part due to SO coupling (M. Kaupp, unpublished results).
19. M. Kaupp, V. G. Malkin, and O. L. Malkina, in Encyclopedia of Computational Chemistry, edited by P. v. R. Schleyer (Wiley, New York, 1998).
20. For the first suggestion of this analogy, see Y. Nomura, Y. Takeuchi, and N. Nakagawa, Tetrahedron Lett, 8, 639 (1969).
21. 13C-NMR-Spectroscopy (Wiley, New York, 1988).
22. 31P-NMR-Spektroskopie (Thieme, Stuttgart, 1993), Vol. 3.
23. 4 molecules in the vapor, extrapolated to zero density; G. Heckmann and E. Fluck, Mol. Phys. 23, 75 (1972).
24. 6. This is at least in part due to SO effects from three heavy tin substituents on phosphorus; M. Driess, S. Martin, V. Pintschouk, H. Pritzkow, H. Grützmacher, and M. Kaupp, Angew. Chem. 109, 1982 (1997); Angew. Chem. Int. Ed. Engl. 36, 1894 (1997).
25. 6. This is at least in part due to SO effects from three heavy tin substituents on phosphorus; M. Driess, S. Martin, V. Pintschouk, H. Pritzkow, H. Grützmacher, and M. Kaupp, Angew. Chem. 109, 1982 (1997); Angew. Chem. Int. Ed. Engl. 36, 1894 (1997).
26. I. Tornieporth-Oetting and T. Klapötke, J. Chem. Soc. Chem. Commun. 1990, 132.
27. S. Pohl, Z. Allg. Anorg. Chem. 498, 20 (1983).
28. A. Bergner, M. Dolg. W. Küchle, H. Stoll, and H. Preuss, Mol. Phys. 80, 1431 (1993).
29. M. Kaupp, P. v. R. Schleyer, H. Stoll, and H. Preuss, J. Am. Chem. Soc. 113, 6012 (1991).
30. GAUSSIAN 94, Revisions B2, G.2, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, and J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1995.
31. V. G. Malkin, O. L. Malkina, M. E. Casida, and D. R. Salahub, J. Am. Chem. Soc. 116, 5898 (1994).
32. W. Kutzelnigg, U. Fleischer, and M. Schindler, in NMR-Basic Principles and Progress Vol. 23 (Springer, Heidelberg, 1990), p. 165ff.
33. J. P. Perdew and Y. Wang, Phys. Rev. B 45, 13244 (1992); J. P. Perdew, in Electronic Structure of Solids, edited by P. Ziesche and H. Eischrig (Akademie Verlag, Berlin, 1991); J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, Phys. Rev. B 46, 6671 (1992).
34. J. P. Perdew and Y. Wang, Phys. Rev. B 45, 13244 (1992); J. P. Perdew, in Electronic Structure of Solids, edited by P. Ziesche and H. Eischrig (Akademie Verlag, Berlin, 1991); J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, Phys. Rev. B 46, 6671 (1992).
35. J. P. Perdew and Y. Wang, Phys. Rev. B 45, 13244 (1992); J. P. Perdew, in Electronic Structure of Solids, edited by P. Ziesche and H. Eischrig (Akademie Verlag, Berlin, 1991); J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, Phys. Rev. B 46, 6671 (1992).
36. deMon program, D. R. Salahub, R. Fournier, P. Mlynarski, I. Papai, A. St-Amant, and J. Ushio, in Density Functional Methods in Chemistry, edited by J. Labanowski and J. Andzelm (Springer, New York, 1991);
37. A. St-Amant and D. R. Salahub, Chem. Phys. Lett. 169, 387 (1990).
38. C. Edmiston and K. Ruedenberg, Rev. Mod. Phys. 35, 457 (1963): J. Chem. Phys. 43, 597 (1965); S. F. Boys, in Quantum Theory of Atoms, Molecules and the Solid State, edited by P. O. Löwdin (Academic, New York, 1996), p. 253ff; This procedure is often erroneously attributed to J. M. Foster and S. F. Boys, Rev. Mod. Phys. 35, 457 (1963).
39. C. Edmiston and K. Ruedenberg, Rev. Mod. Phys. 35, 457 (1963): J. Chem. Phys. 43, 597 (1965); S. F. Boys, in Quantum Theory of Atoms, Molecules and the Solid State, edited by P. O. Löwdin (Academic, New York, 1996), p. 253ff; This procedure is often erroneously attributed to J. M. Foster and S. F. Boys, Rev. Mod. Phys. 35, 457 (1963).
40. C. Edmiston and K. Ruedenberg, Rev. Mod. Phys. 35, 457 (1963): J. Chem. Phys. 43, 597 (1965); S. F. Boys, in Quantum Theory of Atoms, Molecules and the Solid State, edited by P. O. Löwdin (Academic, New York, 1996), p. 253ff; This procedure is often erroneously attributed to J. M. Foster and S. F. Boys, Rev. Mod. Phys. 35, 457 (1963).
41. C. Edmiston and K. Ruedenberg, Rev. Mod. Phys. 35, 457 (1963): J. Chem. Phys. 43, 597 (1965); S. F. Boys, in Quantum Theory of Atoms, Molecules and the Solid State, edited by P. O. Löwdin (Academic, New York, 1996), p. 253ff; This procedure is often erroneously attributed to J. M. Foster and S. F. Boys, Rev. Mod. Phys. 35, 457 (1963).
42. C. J. Jameson, A. de Dios, and A. K. Jameson, Chem. Phys. Lett. 167, 575 (1990).
43. O. L. Malkina, B. Schimmelpfennig, M. Kaupp, B. A. Hess, P. Chandra, U. Wahlgren, and V. G. Malkin, Chem. Phys. Lett. 296, 93 (1998).
44. J. P. Perdew, Phys. Rev. B 33, 8822 (1986); J. P. Perdew and Y. Wang, ibid. 33, 8800 (1986).
45. J. P. Perdew, Phys. Rev. B 33, 8822 (1986); J. P. Perdew and Y. Wang, ibid. 33, 8800 (1986).
46. R. J. Gillespie, M. J. Morton, and J. M. Sowa, Adv. Raman. Spectrosc. 1, 539 (1972).
47. 6 , W. Gabes and K. Olie, Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. 26, 443 (1970).
48. Cf. e.g., K. B. Dillon, M. G. Craveirinha Dillon, and T. C. Waddington, J. Inorg. Nucl. Chem. 38, 1149 (1976).
49. G. Engelhardt, Ch. Aubauer, T. M. Klapotke, and M. Kaupp (unpublished results).
50. 4 (Ref. 18) are somewhat less than half the way between the sum of the van der Waals radii (∼3.90-4.20 Å) and a single bond (∼2.66 Å); See, e.g., J. E. Huheey, E. A. Keiter, and R. L. Keiter, Inorganic Chemistry (Harper&Collins, New York, 1993).
51. W. J. Casteel, Jr., P. Kolb, N. LeBlond, H. P. A. Mercier, and G. J. Schrobilgen, Inorg. Chem. 35, 929 (1996).
52. See, e.g., A. Schäfer, C. Huber, and R. Ahlrichs, J. Chem. Phys. 100, 5829 (1994).
53. See, e.g., U. Fleischer, M. Schindler, and W. Kutzelnigg, J. Chem. Phys. 86, 6337 (1987).
54. See, e.g., E. Kraka, C. P. Sosa, J. Gräfenstein, and D. Cremer, Chem. Phys. Lett. 279, 9 (1997), and references cited therein.
55. In the absence of SO effects, isolated, coordinatively unsaturaled cations with low-lying empty orbitals tend to exhibit large paramagnetic contributions to the central-atom chemical shifts. These are dimished by donation into the empty orbitals due to counteranions and/or solvent molecules, leading usually to lower shifts.
56. N. G. Feshchenko, V. G. Kostina, and A. V. Kirsanov, Zh. Obshch. Khim. 48, 222 (1978).
57. The negative sign given in the original publication (Ref. 40) was later removed, V. G. Kostina, Zh. Obshch. Khim. 51, 1962 (1981).
58. For NMR data, see, K. B. Dillon, M. B. Nisbet, and T. C. Waddington, J. Chem. Soc. Dalton Trans. 1978, 1455.