Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Ab initio Studies on d8-MCI(PH3)2(C2H2), M=Rh and Ir, Complexes

  • Kang, Sung-Kwon (Department of Chemistry, Chungnam National Universtiy) ;
  • Song, Jin-Soo (Department of Chemistry, Chungnam National Universtiy) ;
  • Moon, Jung-Hyun (Department of Chemistry, Chungnam National Universtiy) ;
  • Yun, Sock-Sung (Department of Chemistry, Chungnam National Universtiy)
  • Published : 1997.01.20
Download PDF
⟨ Previous Next ⟩

Abstract

The geometries and energies of the isomers in alkyne complexes MCl(PH3)2(η2-C2H2), M=Rh and Ir, are theoretically investigated using ab initio methods at the Hartree-Fock and up to MP4 level of theory and relativistic effective core potentials for Rh and Ir metals. The optimized structures of Rh complexes, 1-3 at MP2/ECP1 level are in good agreement with the related experimental data. The binding energies of C2H2 to d8-metal fragments are computed to be ∼55 kcal/mol. The vinylidene complexes for Rh and Ir metals are calculated to be much lower in energy than the alkyne complexes. The alkyne-vinylidene rearrangement is possible to proceed exothermically through the intermediate hydrido-alkynyl complexes, 2 or 9. Detailed comparison is given about the geometries and relative energies on Rh and Ir isomers at the various level ab initio calculations with orbital analysis.

Keywords

References

  1. Angew. Chem. Int. Ed. Engl. v.29 Werner, H.
  2. Chem. Rev. v.91 Bruce, M. I.
  3. J. Organomet. Chem. v.448 Braun, T.;Steinert, P.;Werner, H.
  4. J. Organomet. Chem. v.448 Hodge, A. J.;Ingham, S. L.;Kakkar, A. K.;Kan, M. S.;Lewis, J.;Long, N. J.;Parker, D. G.;Raithby, P. R.
  5. Organometallics v.15 Grunwald, C.;Gevert, O.;Wolf, J.;Gonzalez-Herrero, P.;Werner, H.
  6. J. Am. Chem. Soc. v.115 Stegmann, R.;Neuhaus, A.;Frenking, G.
  7. Helv. Chim. Acta v.68 Silverstre, J.;Hoffmann, R.
  8. Angew. Chem., Int. Ed. Engl. v.24 Alonso, F. J. G.;Hohn, A.;Wolf, J.;Otto, H.;Werner, H.
  9. Angew. Chem., Int. Ed. Engl. v.30 Schneider, D.;Werner, H.
  10. Organometallics v.13 Werner, H.;Rappert, T.;Wiedemann, R.;Wolf, J.;Mahr, N.
  11. J. Inorg. Chem. v.32 Chin, C. S.;Yoon, J.;Song, J.
  12. Organometallics v.12 Bianchini, C.;Barbaro, P.;Meli, A.;Peruzzini, M.;Vacca, A.;Vizza, F.
  13. Organometallics v.13 Rahim, M.;Bushweller, C. H.;Ahmed, K. J.
  14. Organometallics v.13 Werner, H.;Baum, M.;Schneider, D.;Windmuller, B.
  15. Organometallics v.14 Werner, H.;Gevert, O.;Steinert, P.;Wolf, J.
  16. Kang, S. K.;Song, J. S.;Moon, J. H.;Yun, S. S.
  17. Frisch, M. J.;Trucks, G. W.;Schlegel, H. B.;Gill, P. M. W.;Johnson, B. G.;Robb, M. A.;Cheeseman, J. R.;Keith, T. A.;Petersson, G. A.;Montgomery, J. A.;Raghavachari, K.;Al-Laham, M. A.;Zakrzewski, V. G.;Ortiz, J. B.;Foresman, J.;Cioslowski, B.;Stefanov, B.;Nanayakkara, A.;Challacombe, M.;Peng, C. Y.;Ayala, W.;Chen, W.;Wong, M. W.;Andres, J. L.;Replogle, E. S.;Gomperts, R.;Martin, R. L.;Fox, D. J.;Binkley, J. S.;Defrees, D. J.;Baker, J.;Stewart, J. P.;Head-Gordon, M.;Gonzalez, C.;Pople, J. A.
  18. J. Chem. Phys. v.82 Hay, P. J.;Wadt, W. R.
  19. J. Chem. Phys. v.82 Wadt, W. R.;Hay, P. J.
  20. J. Am. Chem. Soc. v.102 Binkley, J. S.;Pople, J. A.;Hehre, W. J.
  21. J. Chem. Phys. v.51 Hehre, W. J.;Stewart, R. F.;Pople, J. A.
  22. J. Chem. Phys. v.82 Hay, P. J.;Wadt, W. R.
  23. Theor. Chim. Acta v.28 Hariharan, P. C.;Pople, J. A.
  24. J. Chem. Soc., Dalton Trans. Busetto, C.;D'Alfonso, A.;Maspero, F.;Perego, G.;Zazetta, A.
  25. J. Organomet. Chem. v.139 Hietkamp, S.;Stufkens, D. J.;Vrieze, K.
  26. J. Organomet. Chem. v.287 Werner, H.;Wolf, J.;Hohn, A.
  27. J. Chem. Soc., Chem. Commun. Hohn, A.;Otto, H.;Dziallas, M.;Werner, H.
  28. J. Am. Chem. Soc. v.102 Stockis, A.;Hoffmann, R.
  29. J. Croat. Chim. Acta Kang, S. K.;Albright, T. A.;Silvestre
  30. Orbital Interactions in Chemistry Albright, T. A.;Burdett, J. K.;Whangbo, M.-H.
  31. J. Am. Chem. Soc. v.115 Koga, N.;Morokuma, K.
  32. J. Am. Chem. Soc. v.116 Lin, Z.;Hall, M. B.
  33. Organometallics v.14 Yoshida, T.;Koga, N.;Morokuma, K.
  34. Organometallics v.15 Ehlers, A. W.;Dapprich, S.;Vyboishchikov, S. F.;Frenking, F.
  35. Chem. Ber. v.127 Baum, M.;Mahr, N.;Werner, H.
  36. Angew. Chem. Int. Ed. Engl. v.95 Wolf, J.;Werner, H.;Serhadli, O.;Ziegler, M. L.
  37. Angew. Chem. Int. Ed. Engl. v.22