Steric and electronic effects on the 103Rh NMR chemical shifts of Rh1(cyclooctadiene) compounds bearing N-donor ligands

European Journal of Inorganic Chemistry

Volumn , Issue 1, 1999, Pages 27-33

  Donkervoort, Johannes G ^a   Bühl, Michael ^b   Ernsting, Jan Meine ^a   Elsevier, Cornelis J ^a  

^a UNIVERSITY OF AMSTERDAM   (Netherlands)

^b UNIVERSITY OF ZURICH   (Switzerland)

Author keywords

103Rh NMR; Chemical shift computation; Nitrogen ligands; Rhodium complexes

Indexed keywords

CHLORINE COMPOUNDS; COMPUTATION THEORY; DENSITY FUNCTIONAL THEORY; LIGANDS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; RHODIUM COMPOUNDS;

103RH NMR; CHEMICAL-SHIFT COMPUTATION; ELECTRONIC EFFECTS; EXPERIMENTAL VALUES; N-DONOR LIGANDS; NITROGEN LIGAND; NMR CHEMICAL SHIFTS; NMR SPECTRUM; RHODIUM COMPLEXES; STERIC EFFECT;

CHEMICAL SHIFT;

LIGAND; NITROGEN; RHODIUM COMPLEX;

ANALYTIC METHOD; ARTICLE; CALCULATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 2442763932     PISSN: 14341948     EISSN: None     Source Type: Journal    
DOI: 10.1002/(sici)1099-0682(199901)1999:1<27::aid-ejic27>3.0.co;2-4     Document Type: Article

References (49)

1. R. Benn in: P. S. Pregosin (Ed.), Transition Metal Nuclear Magnetic resonance, Elsevier; Amsterdam, 1991; p. 103.
2. B. E. Mann in: P. S. Pregosin (Ed.), Transition Metal Nuclear Magnetic resonance, Elsevier; Amsterdam, 1991; p. 177.
3. N. F. Ramsey, Phys. Rev. 1950, 77, 567.
4. N. F. Ramsey, Phys. Rev. 1950, 78, 699.
5. N. F. Ramsey, Phys. Rev. 1951, 83, 540.
6. N. F. Ramsey, Phys. Rev. 1952, 86, 243.
7. J. S. Griffith, L. E. Orgel, Trans. Faraday Soc. 1957, 53, 601.
8. J. Mason, Chem. Rev. 1987, 87, 1299.
9. R. Bonnaire, D. Davoust, N. Platzer, Org. Magn. Reson. 1984, 22, 80.
10. J. M. Ernsting, C. J. Elsevier, W. G. de Lange, J. Chem. Soc., Chem. Commun. 1989, 585.
11. C. J. Elsevier, B. Kowall, H. Kragten, Inorg. Chem. 1995, 34, 4836.
12. G. Schreckenbach, T. Ziegler, J. Chem. Phys. 1995, 99, 606.
13. M. Bühl, Chem. Phys. Lett. 1997, 267, 251.
14. Review: M. Bühl, M. Kaupp, V. G. Malkin, O. L. Malkina, J. Comput. Chem., in press.
15. M. Bühl, Organometallics 1997, 16, 261.
16. W. Leitner, M. Bühl, R. Fornika, C. Six, W. Baumann, E. Dinjus, M. Kessler, C. Krüger, A. Rufinska, submitted for publication.
17. K. D. Gruninger, A. Schwenk, B. E. Mann, J. Magn. Reson. 1980, 41, 354.
18. M. A. Garralda, L. Ibarlucea, J. Organometal. Chem. 1986, 311, 225.
19. M. A. Garcia, M. A. Garralda, L. Ibarlucea, Polyhedron 1988, 7, 1067.
20. J. M. Ernsting, C. J. Elsevier, W. G. J. de Lange, K. Timmer, Magn. Res. Chem. 1991, 29, S118.
21. No solid-state structures for the series 1, 2, and 6 are published; steric effects similar to those discussed here, however, can be noted in a cationic Rh(COD) complex with N-(2-aminoethyl)-piperidine as ligand (E. Anzuela, M. A. Garralda, R. Hernandez, L. Ibarlucea, E. Pinilla, M. A. Monge, Inorg. Chim. Acta, 1991, 185, 211): the Rh-N bond lengths to the primary and tertiary amine N atoms, 2.107(6) and 2.176(7) Å, respectively, are shorter than the corresponding DFT data in Table 3 (cf. entries for 1 and 6), but the difference between these distances is very similar in both cases, ca. 7 pm elongation from primary to tertiary amine.
22. Somewhat counterintuitively, roughly the same effect is seen for 2 and 6 upon substituting two and four Me groups, respectively.
23. For similar arguments see for instance: [14a] Y. Ruiz-Morales, G. Schreckenbach, T. Ziegler, J. Phys. Chem. 1996, 100, 3359. [14b] Y. Ruiz-Morales, G. Schreckenbach, T. Ziegler, Organometallics 1996, 15, 3920.
24. For similar arguments see for instance: [14a] Y. Ruiz-Morales, G. Schreckenbach, T. Ziegler, J. Phys. Chem. 1996, 100, 3359. [14b] Y. Ruiz-Morales, G. Schreckenbach, T. Ziegler, Organometallics 1996, 15, 3920.
25. Similar characteristics (i.e. ligand-π* character and contributions from the metal) have been computed for the LUMO of other DAB complexes, which is important for their UV/vis spectra, see for instance 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.
26. S. Braun, H.-O. Kalinowski, S. Berger, in 100 and More Basic NMR Experiments. 1994, 360-363.
27. R. E. Hurd, B. K. John, J. Magn. Reson. 1991, 91, 648-653.
28. J. Ruiz-Cabello, G. W. Vuister, C. T. Moonen, P. van Gelderen, J. S. Cohen, P. C. M. van Zijl, J. Magn. Reson. 1992, 100, 281-303.
29. W. Wilker, D. Leibfritz, R. Kerssebaum, W. Bermel, Magn. Reson. Chem. 1993, 31, 287-292.
30. C. Cocevar, G. Mestroni, A. Camus, J. Organometal. Chem. 1972, 35, 389.
31. R. Uson, L. A. Oro, C. Claver, M. A. Garralda, J. Organometal. Chem. 1976, 105, 365.
32. L. A. Oro, M. J. Fernandez, J. Modrego, J. M. Lopez, J. Organometal. Chem. 1985, 287, 409.
33. P. H. M. Budzelaar, R. de Gelder, A. W. Gal, Organometallics 1998, 17, 4121.
34. Ch. Mahabiersing, J. G. Donkervoort, C. J. Elsevier, in preparation.
35. L. A. Oro, M. A. Ciriano, F. Viguri, C. Foces-Foces, F. H. Cano, Inorg. Chim. Acta 1986, 115, 65.
36. A. van der Ent, A. L. Onderdelinden, Inorg. Synth. 1990, 28, 90.
37. R. Cramer, J. Am. Chem. Soc. 1964, 86, 217.
38. R. Uson, L. A. Oro, M. A. Ciriano, F. J. Lahoz, J. Organometal. Chem. 1982, 240, 429.
39. A. D. Becke, Phys. Rev. A 1988, 38, 3098.
40. J. P. Perdew, Phys. Rev. B 1986, 33, 8822.
41. J. P. Perdew, Phys. Rev. B 1986, 34, 7406.
42. D. Andrae, U. Häußermann, M. Dolg. H. Stoll, H. Preuß, Theor. Chim. Acta 1990, 77, 123.
43. WJ. Hehre, L. Radom, P. v. R. Schleyer, J. A. Pople, Ab initio Molecular Orbital Theory, Wiley, New York, 1986.
44. As implemented in Gaussian 94: J. R. Cheeseman, G. W. Trucks, T. A. Keith and M. J. Frisch, J. Chem. Phys. 1996, 104, 5497.
45. A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
46. C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785.
47. S. Huzinaga, M. Klobukowski, J. Mol. Struct. 1988, 167, 1.
48. W. Kutzelnigg, U. Fleischer, M. Schundler, in NMR Basic Principles and Progress Vol. 23, Springer-Verlag, Berlin, 1990, 165.
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. De Frees, J. Baker, J. J. P. Stewart, M. Head-Gordon, C. Gonzales, J. A. Pople, Gaussian 94, Pittsburgh PA, 1995.