A bis(thiophosphinoyl)methanediide palladium complex: Coordinated dianion or nucleophilic carbene complex?

Angewandte Chemie - International Edition

Volumn 43, Issue 46, 2004, Pages 6382-6385

  Cantat, Thibault ^a   Mézailles, Nicolas ^a   Ricard, Louis ^a   Jean, Yves ^a   Le Floch, Pascal ^a  

^a LABORATOIRE HÉTÉROÉLÉMENTS ET COORDINATION   (France)

Author keywords

Carbenes; Density functional calculations; Palladium; Phosphorus; Sulfides

Indexed keywords

COMPLEXATION; DISCRETE FOURIER TRANSFORMS;

BIS(THIOPHOSPHINOYL)METHANEDIIDE PALLADIUM COMPLEX; CARBENE COMPLEXES; NONBOUNDING ORBITAL;

PALLADIUM COMPOUNDS;

CARBENOID; COORDINATION COMPOUND; LIGAND; PALLADIUM COMPLEX;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL STRUCTURE; DENSITY FUNCTIONAL THEORY; ELECTRON TRANSPORT; MOLECULAR INTERACTION; STRUCTURE ANALYSIS;

EID: 11144254368     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200461392     Document Type: Article

References (48)

1. See for example: a) A. J. Arduengo III, Acc. Chem. Res. 1999, 32, 913-921; b) W. A. Herrmann, T. Weskamp, V. P. W. Bohm, Adv. Organomet. Chem. 2001, 48, 1-69; c) W. A. Herrmann, Angew. Chem. 2002, 114, 1342-1363; Angew. Chem. Int. Ed. 2002, 41, 1290-1309.
2. See for example: a) A. J. Arduengo III, Acc. Chem. Res. 1999, 32, 913-921; b) W. A. Herrmann, T. Weskamp, V. P. W. Bohm, Adv. Organomet. Chem. 2001, 48, 1-69; c) W. A. Herrmann, Angew. Chem. 2002, 114, 1342-1363; Angew. Chem. Int. Ed. 2002, 41, 1290-1309.
3. See for example: a) A. J. Arduengo III, Acc. Chem. Res. 1999, 32, 913-921; b) W. A. Herrmann, T. Weskamp, V. P. W. Bohm, Adv. Organomet. Chem. 2001, 48, 1-69; c) W. A. Herrmann, Angew. Chem. 2002, 114, 1342-1363; Angew. Chem. Int. Ed. 2002, 41, 1290-1309.
4. See for example: a) A. J. Arduengo III, Acc. Chem. Res. 1999, 32, 913-921; b) W. A. Herrmann, T. Weskamp, V. P. W. Bohm, Adv. Organomet. Chem. 2001, 48, 1-69; c) W. A. Herrmann, Angew. Chem. 2002, 114, 1342-1363; Angew. Chem. Int. Ed. 2002, 41, 1290-1309.
5. D. Bourissou, O. Guerret, F. P. Gabbai, G. Bertrand, Chem. Rev. 2000, 100, 39-91.
6. See for example: a) J. Ruiz, M. E. G. Mosquera, G. Garcia, E. Patron, V. Riera, S. Garcia-Granda, F. Van der Maelen, Angew. Chem. 2003, 115, 4915-4919; Angew. Chem. Int. Ed. 2003, 42, 4767-4771;
7. See for example: a) J. Ruiz, M. E. G. Mosquera, G. Garcia, E. Patron, V. Riera, S. Garcia-Granda, F. Van der Maelen, Angew. Chem. 2003, 115, 4915-4919; Angew. Chem. Int. Ed. 2003, 42, 4767-4771;
8. b) T. Cantat, N. Mézailles, N. Maigrot, L. Ricard, P. Le Floch, Chem. Commun. 2004, 1274-1275.
9. + exist as free species, see: M. Soleilhavoup, A. Baceiredo, O. Treutler, R. Ahlrichs, M. Nieger, G. Bertrand, J. Am. Chem. Soc. 1992, 114, 10959-10961.
10. a) R. G. Cavell, R. P. Kamalesh Babu, A. Kasani, R. McDonald, J. Am. Chem. Soc. 1999, 121, 5805-5806;
11. b) R. P. Kamalesh Babu, R. McDonald, S. A. Drecker, M. Klobukowski, R. G. Cavell, Organometallics 1999, 18, 4226-4229;
12. c) R. P. Kamalesh Babu, R. McDonald, R. G. Cavell, Organometallics 2000, 19, 3462-3465;
13. d) K. Aparana, M. Ferguson, R. G. Cavell, J. Am. Chem. Soc. 2000, 122, 726-727;
14. e) R. G. Cavell, R. Kamalesh Babu, K. Aparana, J. Organomet. Chem. 2001, 617-618, 158-169;
15. f) K. Aparana, R. P. Kamalesh Babu, R. McDonald, R. G. Cavell, Angew. Chem. 2001, 113, 4535-4537; Angew. Chem. Int. Ed. 2001, 40, 4400-4402;
16. f) K. Aparana, R. P. Kamalesh Babu, R. McDonald, R. G. Cavell, Angew. Chem. 2001, 113, 4535-4537; Angew. Chem. Int. Ed. 2001, 40, 4400-4402;
17. g) N. D. Jones, G. Lin, R. A. Gossage, R. McDonald, R. C. Cavell, Organometallics, 2003, 22, 2832-2841;
18. h) G. Lin, N. D. Jones, A. Gossage, R. McDonald, R. G. Cavell, Angew. Chem. 2003, 115, 4188-4191;
19. Angew. Chem. Int. Ed. 2003, 42, 4054-4057.
20. a) M. Doux, C. Bouet, N. Mézailles, L. Ricard, P. Le Floch, Organometallics 2002, 21, 2785-2788;
21. b) M. Doux, N. Mézailles, M. Melaïmi, L. Ricard, P. LeFloch, Chem. Commun. 2002, 1566-1567;
22. c) M. Doux, N. Mézailles, L. Ricard, P. LeFloch, Eur. J. Inorg. Chem. 2003, 3878-3894;
23. d) M. Doux, N. Mézailles, L. Ricard, P. Le Floch, Organometallics 2003, 22, 4624-4626;
24. e) M. Doux, L. Ricard, F. Mathey, P. Le Floch, N. Mézailles, Eur. J. Inorg. Chem. 2003, 687-698.
25. N. Matsumura, J.-I. Kawano, N. Fukunishi, H. Inoue, J. Am. Chem. Soc. 1995, 117, 3623.
26. a) A. Kasani, R. P. Kamalesh Babu, R. McDonald, R. G. Cavell, Angew. Chem. 1999, 111, 1580-1582; Angew. Chem. Int. Ed. 1999, 38, 1483-1484;
27. a) A. Kasani, R. P. Kamalesh Babu, R. McDonald, R. G. Cavell, Angew. Chem. 1999, 111, 1580-1582; Angew. Chem. Int. Ed. 1999, 38, 1483-1484;
28. b) C. M. Ong, D.W. Stephan, J. Am. Chem. Soc. 1999, 121, 2939-2940.
29. 3. Crystal data for 4 are given in the Supporting Information. CCDC-245083 (3) and CCDC-245084 (4) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, UK; fax: (+44) 1223-336-033; or deposit@ccdc.cam.ac.uk).
30. See for example: a) A. T. Vincent, P. J. Wheatley, J. Chem. Soc. Dalton Trans. 1972, 617-622; b) G. E. Hardy, J. I. Zink, W. C. Kaska, J. C. Baldwin, J. Am. Chem. Soc. 1978, 100, 8001-8002;
31. See for example: a) A. T. Vincent, P. J. Wheatley, J. Chem. Soc. Dalton Trans. 1972, 617-622; b) G. E. Hardy, J. I. Zink, W. C. Kaska, J. C. Baldwin, J. Am. Chem. Soc. 1978, 100, 8001-8002;
32. c) W. Petz, F. Weller, J. Uddin, G. Frenking, Organometallics 1999, 18, 619-626.
33. a) Gaussian03 (Revision A.1), M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 2003;
34. b) The authors wish to thank the IDRIS center (University Paris-Sud XI Orsay, Institut du développement et des ressources en Informatiques Scientifique) for computational facilities.
35. [21] was used for the Pd atom. The same combination of basis set was chosen for calculation of the theoretical structure of 4 but the 6-31 + G* basis set was used the H atoms of the methyl group.
36. [22] For the theoretical structure of 4, the 6-314 + G* basis set was used for calculating the H atoms of the methyl group.
37. An X-ray crystal analysis of a pyramidalized carbanion has been recently reported: F. Breher, J. Grunenberg, S. C. Lawrence, P. Mountford, H. Rüegger, Angew. Chem. 2004, 116, 2575-2578; Angew. Chem. Int. Ed. 2004, 43, 2521-2524.
38. An X-ray crystal analysis of a pyramidalized carbanion has been recently reported: F. Breher, J. Grunenberg, S. C. Lawrence, P. Mountford, H. Rüegger, Angew. Chem. 2004, 116, 2575-2578; Angew. Chem. Int. Ed. 2004, 43, 2521-2524.
39. Complexes with an H atom replacing the methyl group have already been synthesized by trapping reactions of bis(iminophosphorano)methanide anions with transition-metals fragments. a) S. Al-Benna, M. J. Sarsfield, M. Thornton-Pett, D. L. Ormsby, P. J. Maddox, P. Brès, M. Bochmann, J. Chem. Soc. Dalton Trans. 2000, 4247-4257;
40. b) D. A. Evans, M. S. Hill, P. B. Hitchcock, Dalton Trans. 2003, 570-574.
41. A. Altomare, M. C. Burla, M. Camalli, G. Cascarano, C. Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori, R. Spagna, SIR97, an integrated package of computer programs for the solution and refinement of crystal structures using single crystal data, 1999.
42. M. Sheldrick, SHELXL-97, Universität Göttingen, Göttingen, Germany, 1998.
43. a) A. D. J. Becke, J. Chem. Phys. 1993, 98, 5648-5662;
44. b) J. P. Perdew, Y. Wang, Phys. Rev. B 1992, 45, 13244-13249.
45. A. K. Rappé, C. J. Casewitt, K. S. Colwell, W. A. Goddard, W. M. Skiff, J. Am. Chem. Soc. 1992, 114, 10024-10035.
46. P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299-310.
47. A. W. Ehlers, M. Böhme, S. Dapprich, A. Gobbi, A. Höllwarth, V. Jonas, K. F. Köhler, R. Stegman, A. Veldkamp, G. Frenking, Chem. Phys. Lett. 1993, 208, 111-113.
48. A. E. Reed, L. A. Curtiss, F. Weinhold, Chem. Rev. 1988, 88, 899-926.