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.
Original language | English (US) |
---|---|
Pages (from-to) | 9971-9977 |
Number of pages | 7 |
Journal | Chemical Science |
Volume | 11 |
Issue number | 36 |
DOIs | |
State | Published - Sep 28 2020 |
ASJC Scopus subject areas
- Chemistry(all)
Fingerprint
Dive into the research topics of 'Orbital energy mismatch engenders high-spin ground states in heterobimetallic complexes'. Together they form a unique fingerprint.Datasets
-
CCDC 2015381: Experimental Crystal Structure Determination
Coste, S. C. (Contributor), Pearson, T. J. (Contributor), Altman, A. B. (Contributor), Klein, R. A. (Contributor), Finney, B. A. (Contributor), Hu, M. Y. (Contributor), Alp, E. E. (Contributor), Vlaisavljevich, B. (Contributor) & Freedman, D. E. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc25n59b, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc25n59b&sid=DataCite
Dataset
-
CCDC 2015379: Experimental Crystal Structure Determination
Coste, S. C. (Contributor), Pearson, T. J. (Contributor), Altman, A. B. (Contributor), Klein, R. A. (Contributor), Finney, B. A. (Contributor), Hu, M. Y. (Contributor), Alp, E. E. (Contributor), Vlaisavljevich, B. (Contributor) & Freedman, D. E. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc25n578, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc25n578&sid=DataCite
Dataset
-
CCDC 2015383: Experimental Crystal Structure Determination
Coste, S. C. (Contributor), Pearson, T. J. (Contributor), Altman, A. B. (Contributor), Klein, R. A. (Contributor), Finney, B. A. (Contributor), Hu, M. Y. (Contributor), Alp, E. E. (Contributor), Vlaisavljevich, B. (Contributor) & Freedman, D. E. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc25n5cd, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc25n5cd&sid=DataCite
Dataset