Issue 36, 2020

Orbital energy mismatch engenders high-spin ground states in heterobimetallic complexes

Abstract

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.

Graphical abstract: Orbital energy mismatch engenders high-spin ground states in heterobimetallic complexes

Supplementary files

Article information

Article type
Edge Article
Submitted
09 iyl 2020
Accepted
31 avq 2020
First published
01 sen 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2020,11, 9971-9977

Orbital energy mismatch engenders high-spin ground states in heterobimetallic complexes

S. C. Coste, T. J. Pearson, A. B. Altman, R. A. Klein, B. A. Finney, M. Y. Hu, E. E. Alp, B. Vlaisavljevich and D. E. Freedman, Chem. Sci., 2020, 11, 9971 DOI: 10.1039/D0SC03777J

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