Density functional calculations of 95Mo NMR chemical shifts: Applications to model catalysts for imine metathesis

Chemistry - A European Journal

Volumn 5, Issue 12, 1999, Pages 3514-3522

  Bühl, Michael ^a,b  

^a UNIVERSITY OF ZURICH   (Switzerland)

^b MAX PLANCK INSTITUT FÜR KOHLENFORSCHUNG   (Germany)

Author keywords

Density functional calculations; Homogeneous catalysis; Metathesis; NMR spectroscopy; Reaction mechanisms

Indexed keywords

IMINE; MOLYBDENUM; MOLYBDENUM COMPLEX;

ARTICLE; CATALYST; CHEMICAL REACTION; MOLECULAR DYNAMICS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STEREOCHEMISTRY;

EID: 0032793865     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3765(19991203)5:12<3514::AID-CHEM3514>3.0.CO;2-U     Document Type: Article

References (92)

1. Review: W. von Philipsborn, Chem. Soc. Rev. 1999, 95-106.
2. See, for example: a) P. DeShong, D. R. Sidler, P. J. Rybczynski, A. A. Ogilvie, W. von Philipsborn, J. Org. Chem. 1989, 54, 5432-5437;
3. b) M. Koller, W. von Philipsborn, Organometallics 1992, 11, 467-468;
4. c) K. Unoura, R. Kikuchi, A. Nagasawa, Y. Kato, Y. Fukuda, Inorg. Chim. Acta 1995, 228, 89-92;
5. d) E. J. Meier, W. Kozminski, A. Linden, P. Lustenberger, W. von Philipsborn, Organometallics 1996, 15, 2469-2477.
6. a) H. Bönnemann, W. Brijoux, R. Brinkmann, W. Meurers, R. Mynott, W. von Philipsborn, T. Egolf, J. Organomet. Chem. 1984, 272, 231-249;
7. b) R. Fornika, H. Görls, B. Seeman, W. Leitner, J. Chem. Soc. Chem. Commun. 1995, 1479-1480.
8. a) M. Bühl, O. L. Malkina, V. G. Malkin, Helv. Chim. Acta 1996, 79, 742-754;
9. b) M. Bühl, Organometallics 1997, 16, 261-267.
10. a) M. Bühl, Angew. Chem. 1998, 110, 153-155; Angew. Chem. Int. Ed. 1998, 37, 142-144;
11. a) M. Bühl, Angew. Chem. 1998, 110, 153-155; Angew. Chem. Int. Ed. 1998, 37, 142-144;
12. b) M. Bühl in Modeling NMR Chemical Shifts (Eds.: J. Facelli, A. DeDios), ACS Symposium Series, Vol. 732, in press.
13. T. Ziegler, Can. J. Chem. 1995, 73, 743-761.
14. For recent reviews see: a) M. Kaupp, V. G. Malkin, O. L. Malkina in The Encyclopedia of Computational Chemistry (Eds.: P. von 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;
15. b) M. Bühl, M. Kaupp, V. G. Malkin, O. L. Malkina, J. Comput. Chem. 1999, 20, 91-105;
16. c) G. Schreckenbach, T. Ziegler, Theor. Chem. Acc. 1998, 99, 71-82.
17. a) G. K. Cantrell, T. Y. Meyer, J. Chem. Soc. Chem. Commun. 1997, 1551-1552;
18. b) G. K. Cantrell, T. Y. Meyer, Organometallics 1997, 16, 5381-5383;
19. c) G. K. Cantrell, T. Y. Meyer, J. Am. Chem. Soc. 1998, 120, 8035-8042.
20. For reviews, see: a) R. R. Schrock, Acc. Chem. Res. 1990, 23, 158 -165;
21. b) C. Pariya, K. N. Jayaprakash, A. Sarkar, Coord. Chem. Rev. 1998, 168, 1-48.
22. See, for example: a) A. K. Rappé, W. A. Goddard, J. Am. Chem. Soc. 1982, 104, 448-456;
23. b) E. Folga, T. Ziegler, Organometallics 1993, 12, 325-337;
24. c) Y.-D. Wu, Z.-H. Peng, J. Am. Chem. Soc. 1997, 119, 8043-8049.
25. M. Bühl, Chem. Phys. Lett. 1997, 267, 251-257.
26. N. Godbout, E. Oldfield, J. Am. Chem. Soc. 1997, 119, 8065-8069.
27. A preliminary account of these results has already been included in ref. [7b].
28. a) M. Minelli, J. H. Enemark, R. T. C. Brownlee, M. J. O'Connor, A. G. Wedd, Coord. Chem. Rev. 1985, 68, 169-278;
29. b) P. S. Pregosin in Transition Metal Nuclear Magnetic Resonance (Ed.: P. S. Pregosin), Elsevier, Amsterdam 1991, pp. 67-81;
30. c) J. Malito, Ann. Rep. NMR Spectrosc. 1997, 33, 151-206.
31. A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100.
32. a) J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824;
33. b) J. P. Perdew, Phys. Rev. B 1986, 34, 7406.
34. D. Andrae, U. Häußermann, M. Dolg, H. Stoll, H. Preuß, Theor. Chim. Acta 1990, 77, 123-141.
35. a) W. J. Hehre, R. Ditchfield, J. A. Pople, J. Chem. Phys. 1972, 56, 2257-2261;
36. b) P. C. Hariharan, J. A. Pople, Theor. Chim. Acta. 1973, 28, 213-222.
37. 6-41(d) for Se, see also: R. C. Binning, L. A. Curtiss, J. Comput. Chem. 1990, 11, 1206-1216.
38. J. R. Cheeseman, G. W. Trucks, T. A. Keith, M. J. Frisch, J. Chem. Phys. 1996, 104, 5497-5509.
39. a) J. J. Perdew in Electronic Structure of Solids (Eds.: P. Ziesche, H. Eischrig), Akademie Verlag, Berlin, 1991;
40. b) J. P. Perdew, Y. Wang, Phys. Rev. B 1992, 45, 13244-13249.
41. A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5642.
42. C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789.
43. S. Huzinaga, M. Klobukowski, J. Mol. Struct. 1988, 167, 1-210.
44. W. Kutzelnigg, U. Fleischer, M. Schindler in NMR Basic Principles and Progress, Vol. 23, Springer, Berlin, 1990, pp. 165-262.
45. For the Se basis set see: a) U. Fleischer, Ph.D. thesis, Universität Bochum, Germany, 1992;
46. b) M. Bühl, W. Thiel, U. Fleischer, W. Kutzelnigg, J. Phys. Chem. 1995, 99, 4000-4007.
47. a) V. G. Malkin, O. L. Malkina, M. E. Casida, D. R. Salahub, J. Am. Chem. Soc. 1994, 116, 5898-5908;
48. b) V. G. Malkin, O. L. Malkina, L. A. Eriksson, D. R. Salahub in Modern Density Funtional Theory (Eds.: J. M. Seminario, P. Politzer), Elsevier, Amsterdam, 1995, pp. 273-347.
49. 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, Gaussian 94, Pittsburgh PA, 1995.
50. a) D. R. Salahub, R. Fournier, P. Mlynaski, I. Papai, A. St.-Amant, J. Ushio in Density Functional Methods in Chemistry (Eds.: J. Labanowski, J. Andzelm), Springer, New York, 1991;
51. b) A. St.-Amant, D. R. Salahub, Chem. Phys. Lett. 1990, 169, 387-392.
52. For 1, see, for example: T. J. R. Weakley, Acta Cryst. 1987, C43, 2221-2222; for 5: M. G. Kanatzidid, D. Coucouvanis, Acta Crystallogr. Sect. C 1983, 39, 835-838; for 6: S. C. O'Neal, J. W: C. Olis, J. Am. Chem. Soc. 1988, 110, 1971-1973; for 11: G. A. Robbins, D. S. Martin, Inorg. Chem. 1984, 23, 2086-2093.
53. For 1, see, for example: T. J. R. Weakley, Acta Cryst. 1987, C43, 2221-2222; for 5: M. G. Kanatzidid, D. Coucouvanis, Acta Crystallogr. Sect. C 1983, 39, 835-838; for 6: S. C. O'Neal, J. W: C. Olis, J. Am. Chem. Soc. 1988, 110, 1971-1973; for 11: G. A. Robbins, D. S. Martin, Inorg. Chem. 1984, 23, 2086-2093.
54. For 1, see, for example: T. J. R. Weakley, Acta Cryst. 1987, C43, 2221-2222; for 5: M. G. Kanatzidid, D. Coucouvanis, Acta Crystallogr. Sect. C 1983, 39, 835-838; for 6: S. C. O'Neal, J. W: C. Olis, J. Am. Chem. Soc. 1988, 110, 1971-1973; for 11: G. A. Robbins, D. S. Martin, Inorg. Chem. 1984, 23, 2086-2093.
55. For 1, see, for example: T. J. R. Weakley, Acta Cryst. 1987, C43, 2221-2222; for 5: M. G. Kanatzidid, D. Coucouvanis, Acta Crystallogr. Sect. C 1983, 39, 835-838; for 6: S. C. O'Neal, J. W: C. Olis, J. Am. Chem. Soc. 1988, 110, 1971-1973; for 11: G. A. Robbins, D. S. Martin, Inorg. Chem. 1984, 23, 2086-2093.
56. M. H. Chisholm, F. A. Cotton, C. A. Murillo, W. W. Reichert, Inorg. Chem. 1977, 16, 1801-1808.
57. S. P. Arnensen, H. M. Seip, Acta Chem. Scand. 1966, 20, 2711-2727.
58. 4]; the Mo-Mo distance is ≈ 1 pm shorter than that in the solid state. See: A. H. Kelley, M. Fink, J. Chem. Phys. 1982, 76, 1407-1416.
59. See also: M. R. Bray, R. J. Deeth, V.J. Paget, P.D. Sheen, Int. J. Quantum Chem. 1996, 61, 85-91.
60. One referee questioned the justification of the use of DFT methods for anionic species; so far no general problems have emerged for NMR properties of related oxo anions [see, for example: a) M. Kaupp, O. L. Malkina, V. G. Malkin, J. Chem. Phys. 1997, 106, 9201-9212;
61. b) G. Schreckenbach, T. Ziegler, Int. J. Quantum Chem. 1997, 61, 899-918]; for a performance of DFT methods for electron affinities see, for example:
62. c) G. S. Tschumper, H. F. Schaefer, J. Chem. Phys. 1997, 107, 2529-2541.
63. SOS-DFPT is UDFT together with the so-called Malkin correction (ref. [27]) which serves to reduce the paramagnetic contributions and, thus, the slope of the regression line (Table 1). While it noticeably improves the values of the chemical shifts of many lighter nuclei, the Malkin correction turns out to be relatively small for the metal shift in Mo compounds; the same has been found previously for Fe chemical shifts (ref. [4a]).
64. H. Nakatsuji, M. Sugimoto, Inorg. Chem. 1990, 29, 1221-1225.
65. J. E. Combariza, J. H. Enemark, M. Barfield, J. C. Facelli, J. Am. Chem. Soc. 1989, 111, 7619-7621.
66. exp slope for 1, 5, 6, and 7 is ≈ 1.66, which, including 10 and 11, is reduced to ≈0.93 and 1.18 at GIAO-BPW91 and GIAO-B3LYP, respectively.
67. 2 is a notorious case for ab initio methods. See, for example: a) H. Stoll, H.-J. Werner, Mol. Phys. 1996, 88, 793-802, and references therein; instabilities in the HF wavefunction of 11 and related species are well-known, for example:
68. b) M. Benard, J. Chem. Phys. 1979, 71, 2546-2556;
69. c) M. B. Hall, Polyhedron 1987, 6, 679-684.
70. 57Fe) of ferrocene, on the other hand, is also a failure for GIAO-HF (and also for pure density functionals), although it was not for GIAO-B3LYP, see ref. [11].
71. The excellent performance of the pure DFT methods for Mo compounds may to some extent be the result of error cancellation between an inherent underestimation of the paramagnetic contributions and an overestimation thereof because of the longer bonds in the optimized geometries; nevertheless, the hybrid method also performs worse when experimental geometries are employed (cf. the regression gradients of 0.93 and 1.18 for GIAO-BPW91 and GIAO-B3LYP, respectively), including the large errors for 10 and 11.
72. See, for example: C. Adamo, V. Barone, Chem. Phys. Lett. 1998, 298, 113-119.
73. V. C. Gibson, C. Redshaw, W. Clegg, M. R. J. Elsegood, J. Chem. Soc. Chem. Commun. 1994, 2635-2636.
74. In order to ensure that TS13a and TS13b connect the minima shown in Figure 3, the relevant parts of the intrinsic reaction coordinate have been followed [a) C. Gonzales, H. B. Schlegel, J. Chem. Phys. 1989, 90, 2154-2161;
75. b) C. Gonzales, H. B. Schlegel, J. Phys. Chem. 1990, 94, 5523-5527].
76. K. Monteyne, T. Ziegler, Organometallics 1998, 17, 5901-5907.
77. VI complexes of the present study, such effects should be small because of the small s character in the bonding. See ref. [7b] and
78. b) M. Kaupp, O. L. Malkina, V. G. Malkin, P. Pyykkö, Chem. Eur. J. 1998, 4, 118-126.
79. Review: A. E. Reed, L. A. Curtiss, F. Weinhold, Chem. Rev. 1988, 88, 899-926.
80. Similar total shieldings are obtained to those from distributed-gauge methods; alternatively, one could analyze the contributions in the GIAO framework; however, the Gaussian 94 program does not provide the corresponding MO analysis.
81. For similar pictorial rationalizations of paramagnetic contributions see ref. [25] and, for example, a) Y. Ruiz-Morales, G. Schreckenbach, T. Ziegler, J. Phys. Chem. 1996, 100, 3359-3367;
82. b) Y. Ruiz-Morales, T. Ziegler, J. Phys. Chem. A 1998, 102, 3970-3976.
83. p contributions not discussed here ; for 18 the x direction is not the most deshielded one any more.
84. 18O) in transition-metal oxo complexes see ref. [35a].
85. See, for example: a) D. Rehder, in Transition Metal Nuclear Magnetic Resonance (Ed. : P. S. Pregosin), Elsevier, Amsterdam, 1991, pp. 1-58;
86. b) R. G. Kidd, Ann. Rep. NMR Spectrosc. 1991, 23, 85-139;
87. c) H. Nakatsuji, Z.-M. Hu, T. Nakajima, Chem. Phys. Lett. 1997, 257, 429-436; in some cases, inverse halogen dependence is also found for late transition metal complexes, for example:
88. d) F. Pichierri, E. Chairparin, E. Zangrando, L. Randaccio, D. Holtenrich, B. Lippert, Inorg. Chim. Acta 1997, 264, 109-116.
89. Main group nuclei usually follow the "normal halogen dependence". See, for example: R. G. Kidd, Ann. Rep. NMR Spectrosc. 1980, 10A, 1-79; see also ref. [47a].
90. See, for example: a) T. G. Appleton, H. C. Clark, L. E. Manzer, Coord. Chem. Rev. 1973, 10, 335-422;
91. b) M. M. Gofmann, V.I. Nefedov, Inorg. Chim. Acta 1978, 28, 1-17.
92. 95Mo) = -504, although it is not more shielded than the fluoro derivative 18 (Table 2).