Bond-stretch isomers of transition-metal complexes. Do they exist? Academic Article uri icon


  • The existence of bond-stretch isomers of transition-metal complexes and the electronic mechanisms explaining these isomers are investigated with ab initio calculations. For (LWOCl2)+ (L = N, N′, N″-trimethyl-1, 4, 7-triazacyclononane) complexes, only the 2A′ state can be identified as a ground state. 2A″ is an excited state, and the orbital crossing mechanism cannot explain the occurrence of two stable isomers. For cis-mer-MoOCl2(PR3)3 complexes, the second-order Jahn-Teller effect is too weak to cause the bond-stretch phenomenon. On both molecular systems, our calculations support the structure of the blue “isomer” as the stable compound and preclude the existence of any other isomer with a long M-O bond and similar energy. © 1991, American Chemical Society. All rights reserved.

author list (cited authors)

  • Song, J., & Hall, M. B.

citation count

  • 20

publication date

  • November 1991