Orbital energy mismatch engenders high-spin ground states in heterobimetallic complexes. Academic Article uri icon


  • The spin state in heterobimetallic complexes heavily influences both reactivity and magnetism. Exerting control over spin states in main group-based heterobimetallics requires a different approach as the orbital interactions can differ substantially from that of classic coordination complexes. By deliberately engendering an energetic mismatch within the two metals in a bimetallic complex we can mimic the electronic structure of lanthanides. Towards this end, we report a new family of complexes, [Ph,MeTpMSnPh3] where M = Mn (3), Fe (4), Co (5), Ni (6), Zn (7), featuring unsupported bonding between a transition metal and Sn which represent an unusual high spin electronic structure. Analysis of the frontier orbitals reveal the desired orbital mismatch with Sn 5s/5p primarily interacting with 4s/4p M orbitals yielding localized, non-bonding d orbitals. This approach offers a mechanism to design and control spin states in bimetallic complexes.

published proceedings

  • Chem Sci

altmetric score

  • 0.25

author list (cited authors)

  • Coste, S. C., Pearson, T. J., Altman, A. B., Klein, R. A., Finney, B. A., Hu, M. Y., ... Freedman, D. E.

citation count

  • 4

complete list of authors

  • Coste, Scott C||Pearson, Tyler J||Altman, Alison B||Klein, Ryan A||Finney, Brian A||Hu, Michael Y||Alp, E Ercan||Vlaisavljevich, Bess||Freedman, Danna E

publication date

  • September 2020