Do ν(CO) stretching frequencies in metal carbonyl complexes unequivocally correlate with the intrinsic electron-donicity of ancillary ligands?

Chemistry - A European Journal

Volumn 17, Issue 24, 2011, Pages 6602-6605

  Valyaev, Dmitry A ^a,b   Brousses, Rémy ^a   Lugan, Noël ^a   Fernández, Israel ^c   Sierra, Miguel A ^c  

^a LCC LABORATOIRE DE CHIMIE DE COORDINATION   (France)

^b A N NESMEYANOV INSTITUTE OF ORGANOELEMENT COMPOUNDS   (Russian Federation)

^c UNIVERSIDAD COMPLUTENSE DE MADRID   (Spain)

Author keywords

AIM theory; carbene complexes; charge density analyses; density functional calculations; IR spectroscopy

Indexed keywords

AIM THEORY; CARBENE COMPLEXES; CHARGE DENSITY ANALYSES; DENSITY-FUNCTIONAL CALCULATIONS; IR SPECTROSCOPY;

CARBONYLATION; COMPLEXATION; MANGANESE; MANGANESE COMPOUNDS;

LIGANDS;

EID: 79957949001     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201100651     Document Type: Article

References (49)

1. E. W. Abel, F. G. A. Stone, Q. Rev. Chem. Soc. 1969, 23, 325-371.
2. W. Strohmeier, F. J. Müller, Z. Naturforsch. B 1967, 22, 451-452
3. W. Strohmeier, F. J. Müller, Chem. Ber. 1967, 100, 2812-2821
4. C. A. Tolman, J. Am. Chem. Soc. 1970, 92, 2953-2956
5. C. A. Tolman, Chem. Rev. 1977, 77, 313-348
6. O. Kuhl, Coord. Chem. Rev. 2005, 249, 693-704
7. R. Dorta, E. D. Stevens, N. M. Scott, C. Costabile, L. Cavalho, C. D. Hoff, S. P. Nolan, J. Am. Chem. Soc. 2005, 127, 2485-2495
8. S. Wolf, H. Plenio, J. Organomet. Chem. 2009, 694, 1487-1492
9. D. G. Gusev, Organometallics 2009, 28, 763-770
10. D. G. Gusev, Organometallics 2009, 28, 6458-6461.
11. E. O. Fischer, E. W. Meineke, F. R. Kreissl, Chem. Ber. 1977, 110, 1140-1147.
12. CCDC-802804, CCDC-802805, CCDC-802806, CCDC-802807 and CCDC-802808 contain full crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via.
13. K. G. Caulton, Coord. Chem. Rev. 1981, 38, 1-61.
14. N. M. Kostić, R. F. Fenske, J. Am. Chem. Soc. 1982, 104, 3879-3884
15. B. E. R. Schilling, R. Hoffmann, D. L. Lichtenberger, J. Am. Chem. Soc. 1979, 101, 585-591.
16. For a definition of syn and anti (Fischer) carbene complexes conformers, see
17. I. Fernández, F. P. Cossío, A. Arrieta, B. Lecea, M. J. Mancheno, M. A. Sierra, Organometallics 2004, 23, 1065-1071
18. D. M. Andrada, M. E. Z. Michoff, I. Fernández, A. M. Granados, M. A. Sierra, Organometallics 2007, 26, 5854-5858.
19. R. F. W. Bader, Atoms in Molecules-A Quatum Theory, Oxford University Press, Oxford, 1990.
20. [9c]
21. C. Jelsch, B. Guillot, A. Lagoutte, C. Lecomte, J. Appl. Crystallogr. 2004, 37, 38-54
22. N. K. Hansen, P. Coppens, Acta Crystallogr. Sect. A 1978, 34, 909-921.
23. A theoretical model of the ED was obtained by single-point calculation on the 100 K X-ray geometry (BP86/def2-TZVPP level). The topology of the ED was conducted using the AIMAll program package (T. A Keith, AIMAll, 2010, http://tkgristmill.com).
24. U. Koch, P. L. A. Popelier, J. Phys. Chem. 1995, 99, 9747-9754.
25. C31 were estimated to 1.70 and 1.85 Å, respectively, upon the analysis of the computed ED of (A)- 2 b -syn (BP86/def2-TZVPP level).
26. E. Espinosa, E. Molins, C. Lecomte, Chem. Phys. Lett. 1998, 285, 170-173
27. E. Espinosa, I. Alkorta, I. Rozas, J. Elguero, E. Molins, Chem. Phys. Lett. 2001, 336, 457-461.
28. bcp)is the potential enegy density (in au)
29. Yu. V. Nelyubina, M. Yu Antipin, K. A. Lyssenko, Russ. Chem. Rev. 2010, 79, 167-187.
30. All calculations were carried out using the Gaussian 09 suite of programs at the BP86/def2-SVP level. Gaussian 09, Revision B.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian, Inc., Wallingford CT, 2009.
31. A similar, albeit smaller, interaction is in part responsible for the anti/syn preference in Group 6 Fischer-type carbene complexes. See reference [7].
32. See, for instance
33. P. A. Hamley, S. G. Kazarian, M. Poliakoff, Organometallics 1994, 13, 1767-1774
34. A. J. Lupinetti, S. Frau, G. Frenking, S. H. Strauss, J. Phys. Chem. A 1997, 101, 9551-9559
35. P. Braunstein, J.-P. Taquet, O. Siri, R. Welter, Angew. Chem. 2004, 116, 6048-6051
36. Angew. Chem. Int. Ed. 2004, 43, 5922-5925
37. P. A. Dub, O. A. Filippov, N. V. Belkova, J.-C. Daran, L. M. Epstein, R. Poli, E. S. Shubina, Dalton Trans. 2010, 39, 2008-2015
38. V. A. Levina, O. A. Filippov, E. I. Gustul, N. V. Belkova, L. M. Epstein, A. Lledõs, E. S. Shubina, J. Am. Chem. Soc. 2010, 132, 11234-11246.
39. CSD version 5.31, 2009.
40. P. Buchgraber, L. Toupet, V. Guerchais, Organometallics 2003, 22, 5144-5147
41. B. R. Galan, M. Gembicky, P. M. Dominiak, J. B. Keister, S. T. Diver, J. Am. Chem. Soc. 2005, 127, 15702-15703
42. H. Sakurai, K. Sugitani, T. Moriuchi, T. Hirao, J. Organomet. Chem. 2005, 690, 1750-1755
43. K. E. Krahulic, G. D. Enright, M. Parvez, R. Roesler, J. Am. Chem. Soc. 2005, 127, 4142-4143
44. G. D. Frey, K. Ofele, H. G. Krist, E. Herdtweck, W. A. Herrmann, Inorg. Chim. Acta 2006, 359, 2622-2634
45. S. A. Llewellyn, M. L. H. Green, A. R. Cowley, Dalton Trans. 2006, 4164-4168
46. S. A. Llewellyn, M. L. H. Green, J. C. Green, A. R. Cowley, Dalton Trans. 2006, 2535-2541
47. S. Kim, S. Y. Choi, Y. T. Lee, K. H. Park, H. Sitzmann, Y. K. Chung, J. Organomet. Chem. 2007, 692, 5390-5394
48. V. César, N. Lugan, G. Lavigne, J. Am. Chem. Soc. 2008, 130, 11286-11287.
49. It is tempting to assume that this interaction affects the ν(CO) stretching frequencies but such an influence cannot be evaluated in that case, due to the cyclic nature of NHC ligands that naturally preclude the existence of the alternative syn conformer.