Density-functional computation of 99Ru NMR parameters

Chemistry - A European Journal

Volumn 6, Issue 17, 2000, Pages 3272-3280

  Bühl, Michael ^a,c   Gaemers, Sander ^b   Elsevier, Cornelis J ^b  

^a UNIVERSITY OF ZURICH   (Switzerland)

^b UNIVERSITY OF AMSTERDAM   (Netherlands)

^c MAX PLANCK INSTITUT FÜR KOHLENFORSCHUNG   (Germany)

Author keywords

Density functional calculations; Electric field gradients; NMR spectroscopy; Quadrupolar relaxation; Ruthenium

Indexed keywords

ORGANOMETALLIC COMPOUND; RUTHENIUM; RUTHENIUM DERIVATIVE;

ARTICLE; ELECTRIC FIELD; GEOMETRY; METAL BINDING; NUCLEAR MAGNETIC RESONANCE; STRUCTURE ACTIVITY RELATION; STRUCTURE ANALYSIS;

EID: 0038748863     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3765(20000901)6:17<3272::aid-chem3272>3.0.co;2-e     Document Type: Article

References (88)

1. a) R. Benn, A. Rufinska, Angew. Chem. 1986, 98, 851-871; Angew. Chem. Int. Ed. Engl. 1986, 25, 861-881;
2. a) R. Benn, A. Rufinska, Angew. Chem. 1986, 98, 851-871; Angew. Chem. Int. Ed. Engl. 1986, 25, 861-881;
3. b) Transition Metal Nuclear Magnetic Resonance (Ed.: P. S. Pregosin), Elsevier, Amsterdam, 1991.
4. W. von Philpsborn, Chem. Soc. Rev. 1999, 28, 95-105.
5. See, for instance: The Encyclopedia of Computational Chemistry (Eds.: P. v. R. Schleyer, N. L. Allinger, T. Clark, J. Gasteiger, P. A. Kollman, H. F. Schaefer III, P. R. Schreiner), Wiley, Chichester, 1998.
6. T. Ziegler, Can. J. Chem. 1995, 73, 743-761.
7. For recent reviews see: a) M. Kaupp, V. G. Malkin, O. L. Malkina, in The Encyclopedia of Computational Chemistry (Eds.: P. v. R. Schleyer, N. L. Allinger, T. Clark, J. Gasteiger, P. A. Kollman, H. F. Schaefer, III, P. R. Schreiner), Wiley, Chichester, 1998, pp. 1857-1866;
8. b) M. Bühl, M. Kaupp, V. G. Malkin, O. L. Malkina, J. Comput. Chem. 1999, 20, 91-105;
9. c) G. Schreckenbach, T. Ziegler, Theor. Chem. Acc. 1998, 99, 71-82.
10. M. Bühl, Chem. Phys. Lett. 1997, 267, 251-257.
11. N. Godbout, E. Oldfield, J. Am. Chem. Soc. 1997, 119, 8065-8069.
12. M. Bühl, F. A. Hamprecht, J. Comput. Chem. 1998, 119, 113-122.
13. M. Bühl, Chem. Eur. J. 1999, 5, 3514-3522.
14. S. Gaemers, J. van Slageren, C. M. O'Connor, J. G. Vos, R. Hage, C. J. Elsevier, Organometallics 1999, 18, 5238-5244.
15. a) M. Bühl, G. Hopp, W. von Philipsborn, S. Beck, M. Prosenc, U. Rief, H.-H. Brintzinger, Organometallics 1996, 15, 778-785;
16. b) M. Bühl, Magn. Reson. Chem. 1996, 34, 782-790.
17. A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100.
18. a) J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824;
19. b) J. P. Perdew, Phys. Rev. B 1986, 34, 7406.
20. D. Andrae, U. Häussermann, M. Dolg, H. Stoll, H. Preuss, Theor. Chim. Acta 1990, 77, 123-141.
21. P. Fuentealba, H. Preuss, H. Stoll, L. von Szentpaly, Chem. Phys. Lett. 1982, 89, 418-422.
22. A. Bergner, M. Dolg, W. Küchle, H. Stoll, H. Preuss, Mol. Phys. 1993, 80, 1431-1441.
23. Valence basis for I taken from: M. Kaupp, P. v. R. Schleyer, H. Stoll, H. Preuss, J. Am. Chem. Soc. 1991, 113, 6012-6020.
24. a) W. J. Hehre, R. Ditchfield, J. A. Pople, J. Chem. Phys. 1972, 56, 2257-2261;
25. b) P. C. Hariharan, J. A. Pople, Theor. Chim. Acta. 1973, 28, 213-222.
26. R. Ahlrichs, M. Bär, M. Häser, H. Korn, M. Kölmel, Chem. Phys. Lett. 1989, 154, 165-169.
27. O. Treutler, R. Ahlrichs, J. Chem. Phys. 1995, 102, 346-354.
28. a) K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 240, 283;
29. b) K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97, 119-124; auxiliary bases have been obtained from Karlsruhe by ftp, see: http://www.chemie.uni-karlsruhe.de/PC/Theochem (SVP-optimized in conjunction with 6-31G* basis).
30. J. R. Cheeseman, G. W. Trucks, T. A. Keith, M. J. Frisch, J. Chem. Phys. 1996, 104, 5497-5509.
31. a) J. P. Perdew, in Electronic Structure of Solids (Eds.: P. Ziesche, H. Eischrig). Akademie, Berlin, 1991;
32. b) J. P. Perdew, Y. Wang, Phys. Rev. B 1992, 45, 13244-13249.
33. A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5642.
34. C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789.
35. S. Huzinaga, M. Klobukowski, J. Mol. Struct. 1988, 167, 1-210.
36. A. J. H. Wachters, J. Chem. Phys. 1970, 52, 1033-1036.
37. W. Kutzelnigg. U. Fleischer, M. Schindler, in NMR Basic Principles and Progress, Vol. 23, Springer, Berlin, 1990, pp. 165-262.
38. Sn and I basis sets are constructed from Huzinaga basis functions, contracted and augmented (no f functions have been included in the present work) to [12s 11p 9d]: a) U. Fleischer, unpublished; these basis sets are constructed analogously to those described in:
39. b) U. Fleischer, Ph.D. thesis, University of Bochum (Germany), 1992;
40. c) M. Bühl, W. Thiel, U. Fleischer, W. Kutzelnigg, J. Phys. Chem. 1995, 99, 4000-4007.
41. a) R. W. Dykstra, A. M. Harrison, J. Magn. Reson. 1982, 46, 338-342;
42. b) C. Brevard, P. Granger, Inorg. Chem. 1982, 22, 532-535.
43. Pb is described with a MEFIT ECP together with a 2s 2s 1d valence basis: W. Küchle, M. Dolg, H. Stoll, H. Preuss, Mol. Phys. 1991, 74, 1245-1263.
44. a) 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. J. P. Stewart, M. Head-Gordon, C. Gonzales, J. A. Pople, Gaussian94, Gaussian, Pittsburgh (PA), 1995;
45. b) M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, R. E. Stratman, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, C. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. G. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzales, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian98, Gaussian, Pittsburgh (PA), 1998.
46. 3);
47. +).
48. +).
49. Compound 6: P. Seiler, J. D. Dunitz, Acta Crystallogr. B 1980, 36, 2946-2950.
50. Compound 7: M. R. Churchill, F. J. Hollander, J. P. Hutchinson, Inorg. Chem. 1977, 16, 2655-2659.
51. -);
52. -);
53. -).
54. a) Compound 10: C. J. Kleverlaan, D. J. Stufkens, J. Fraanje, K. Goubitz, Eur. J. Inorg. Chem. 1998, 1243-1251;
55. b) Compound 12: H. A. Nieuwenhuis, M. C. E. van de Ven, D. J. Stufkens, A. Oskam, K. Goubitz, Organometallics 1995, 14, 780-788;
56. c) Compound 14: M. P. Aarnts, M. P. Wilms, K. Peelen, J. Fraanje, K. Goubitz, F. Hartl, D. J. Stufkens, E. J. Baerends, A. Vlcek, Inorg. Chem. 1996, 35, 5468-5477.
57. See for instance: M. R. Bray, R. J. Deeth, V. J. Paget, P. D. Sheen, Int. J. Quantum Chem. 1996, 61, 85-91.
58. Inclusion of diffuse functions on I (which could improve the description of this anionic system) has almost no effect on the optimized bond lengths. Scalar relativistic effects are included through the pseudopotentials on the heavier elements, which is usually sufficient (see for instance: G. Frenking, I. Antes, M. Böhme, S. Dapprich, A. W. Ehlers, V. Jonas, A. Neuhaus, M. Otto, R. Stegmann, A. Veldkamp, S. F. Vyboishchikov, in Reviews in Computational Chemistry, Vol. 8 (Eds: K. B. Lipkowitz, D. B. Boyd), VCH, New York, 1996, pp. 63-144).
59. See for instance: Y. Zhang, W. Pan, W. Yang, J. Chem. Phys. 1997, 107, 7921-7925.
60. Such effects are apparent e.g. in the thermochemistry of perchloroalkanes: J. Cioslowski, G. Liu, D. Moncrieff, J. Phys. Chem. A 1998, 102, 9965-9969.
61. 4:
62. b) H. Nakatsuji, T. Nakajima, M. Hada, H. Takashima, S. Tanaka, Chem. Phys. Lett. 1995, 247, 418-424.
63. M. Kaupp, O. L. Malkina, V. G. Malkin, P. Pyykkö, Chem. Eur. J. 1998, 4, 118-126.
64. H. Nakatsuji, Z.-M. Hu, T. Nakajima, Chem. Phys. Lett. 1997, 275, 429-436.
65. M. Kaupp, O. L. Malkina, V. G. Malkin, J. Comput. Chem. 1999, 20, 1304-1313.
66. Review: A. E. Reed, L. A. Curtiss, F. Weinhold, Chem. Rev. 1988, 88, 899-926.
67. In fact, an unconstrained NLMO search finds no bonds between Ru and I in 4a; rather, an ionic description results, with lone pairs on I containing small contributions (ca. 15%) from the metal. The s(Ru) contributions mentioned in the text are obtained when a Ru-I bonding MO is enforced using the CHOOSE keyword in Gaussian94; in this option, enforced NLMO populations of ca. 40% and 60% are assigned to Ru and I, respectively.
68. 4 is 31%, with a polarization of the MO towards C (total populations ca. 60% and 40% on C and I, respectively).
69. The relativistic effects of second-row transition-metal nuclei on their own shielding constants are noticeable, but cancel to a large extent when relative chemical shifts, i.e. shielding differences, are considered (see for instance: G. Schreckenbach, T. Ziegler, Int. J. Quantum. Chem. 1997, 61, 899-918), and can thus be neglected for the purposes of this study.
70. This value has been obtained by compressing and elongating the optimized Ru-I bonds by Δr = 5 pm each, leaving all other parameters unchanged, and by a linear fit of the resulting three [r,σ(r)] data points. The Ru nucleus becomes deshielded with increasing Ru-I bond lengths.
71. The Principles of Nuclear Magnetism (Ed.: A. Abragam), Oxford University Press, Oxford, 1961, Chapter 9, p. 314.
72. See for example: a) L. Hemmingsen, U. Ryde, J. Phys. Chem. 1996, 100, 4803-4809;
73. b) V. Kellö, A. Sadlej, P. Pyykkö, D. Sundholm, M. Tokman, Chem. Phys. Lett. 1999, 304, 414-422;
74. c) M. Gee, R. E. Wasylishen, in Modeling NMR Chemical Shifts (Eds.: J. C. Facelli, A. D. deDios), ACS Symp. Ser. 1999, 732, 259-276.
75. See for instance: a) M. Pernpointer, P. Schwerdtfeger, B. A. Hess, Int. J. Quantum Chem. 2000, 76, 371-384;
76. b) V. Kellö, A. J. Sadlej, Phys. Rev. A 1999, 60, 3575-3585;
77. c) V. Kellö, P. Pyykkö, A. J. Sadlej, P. Schwerdtfeger, J. Thyssen, Chem. Phys. Lett. 2000, 318, 222-231, and references cited therein.
78. M. A. Fedotov, O. L. Malkina, V. G. Malkin, Chem. Phys. Lett. 1996, 258, 330-335.
79. Compounds 15, 16: M. P. Aarndts, D. J. Stufkens, A. Oskam, J. Fraanje, K. Goubitz, Inorg. Chim. Acta, 1997, 256, 93-105.
80. zz and Δσ for the whole set of compounds.
81. 2O at room temperature (cf. ref. [30a]).
82. Taken from: F. E. Wagner, U. Wagner, in Mössbauer Isomer Shifts (Eds.: G. K. Shenoy, F. E. Wagner), North Holland, Amsterdam, 1978, pp. 431-514.
83. R. Greatrex, N. N. Greenwood, P. Kaspi, J. Chem. Soc. A 1971, 1873-1877 (see the appendix for an excellent discussion).
84. 2 (CRC Handbook of Chemistry and Physics, 72nd ed., CRC, Boca Raton, 1991).
85. 2 (CRC Handbook of Chemistry and Physics, 72nd ed., CRC, Boca Raton, 1991).
86. In addition to possible shortcomings inherent to the DFT method employed, errors may be introduced by neglect of relativistic effects (which, apparently, amount to just a few percent for nuclei from the 5th period, cf. ref. [54]) and by uncertainties in the experimental nuclear quadrupole moments (see for instance P. Pyykkö, Z. Naturforsch 1992, 47a, 189-196).
87. 4: 1.79 Å and 116.0° (M. D. Silverman, H. A. Levy, J. Am. Chem. Soc. 1954, 76, 3317-3319);
88. 4N]: 1.570(7) Å, 2.310(1) Å, and 104.58(4)° (F. L. Phillips, A. C. Skapski, Acta Crystallogr. 1975, B31, 2667-2670).