DOI QR코드

DOI QR Code

Ab initio Studies on Rh(I)- and Ir(I)-Phenylacetylene Complexes

  • Published : 1998.05.20

Abstract

The structures and energies for the intramolecular rearrangement in $d^8-MCl(PH_3)_2$(HC≡CPh), M=Rh and Ir, complexes were studied by ab initio method at the Hartree-Fock and MP2 levels of theory. Three transition states in two pathways were optimized and characterized by frequency calculations. The activation energies for the process of π-type complex 1 to hydrido-alkynyl 2 have been computed to be relatively low 6.97 and 21.33 kcal/mol at MP2 level for Rh and Ir metals, respectively. However, the activation energies for a 1,2-hydrogen shift via t.s.3 have been computed to be high 50.83 and 60.05 kcal/mol for Rh and Ir metals.

Keywords

References

  1. Organometallics v.16 Chin, C. S.;Lee, H.;Oh, M.
  2. Organometallics v.16 Ahlers, W.;Temme, B.;Erker, G.;Frohlich, R.;Zippel, F.
  3. Organometallics v.15 Lamata, M. P.;Jose, E. S.
  4. Inorg. Chem. v.32 Chin, C. S.;Yoon, J.;Song, J.
  5. J. Organomet. Chem. v.448 Braun, T.;Steinert, P.;Werner, H.
  6. Angew. Chem. Int. Ed. Engl. v.29 Werner, H.
  7. Adv. Organomet. Chem. v.22 Bruce, M. I.;Swingcer, A. G.
  8. Helv. Chim. Acta v.68 Silverstre, J.;Hoffmann, R.
  9. J. Am. Chem. Soc. v.116 Wakatsuk, Y.;Koga, N.;Yamazaki, H.;Morokuma, K.
  10. J. Am. Chem. Soc. v.115 Stemann, R.;Neuhaus, A.;Frenking, G.
  11. J. Organomet. Chem. v.287 Werner, H.;Wolf, J.;Hohn, A.
  12. Angew. Chem. Int. Ed. Engl. v.25 Hohn, A.;Werner, H.
  13. J. Chem. Soc. Chem. Commun. Hohn, A.;Otto, H.;Dziallas, M.;Werner, H.
  14. Naturforsch. B v.43b Werner, H.;Alonso, F. J. G.;Otto, H.;Wolf, J. Z.
  15. Bull. Korean Chem. Soc. v.17 Kang, S. K.;Song, J. S.;Moon, J. H.;Yun, S. S.
  16. Bull. Korean Chem. Soc. v.18 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. B.;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.;Defress, 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. Am. Chem. Soc. v.105 Yoshida, T.;Youngs, W. J.;Sakaeda, T. Ueda, T.;Otsuka, S.;Ibers, J. A.
  23. Organometallics v.13 Werner, H.;Baum, M.;Schneider, D.;Windmuller, B.
  24. J. Am. Chem. Soc. v.119 Wakatsuki, Y.;Koga, N.;Werner, H.;Morokuma, K.