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

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 de...

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Published inChemical science (Cambridge) Vol. 11; no. 36; pp. 9971 - 9977
Main 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
Format Journal Article
LanguageEnglish
Published Cambridge Royal Society of Chemistry 01.01.2020
The Royal Society of Chemistry
Subjects
Bimetals
Bonding
Chemistry
Coordination compounds
Crystallography
Electron spin
Electronic structure
heterobimetallic
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Lanthanides
lathanides
Magnetism
Manganese
NANOSCIENCE AND NANOTECHNOLOGY
Nickel
Orbitals
spin state
Transition metals
Zinc
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Summary: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,Me TpMSnPh 3 ] 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. We report a series of high spin bimetallic transition metal-tin complexes. The unusual high spin configuration in a bimetallic complex is enabled by an energetic mismatch in the orbital energies, leading to lanthanide-like nonbonding interactions.
Bibliography:For ESI and crystallographic data in CIF or other electronic format see DOI
10.1039/d0sc03777j
6
and
7
1-4
can be obtained from the Cambridge Structural Database
Electronic supplementary information (ESI) available: Methods and additional characterization. CCDC Crystallographic information of
2015378-2015383
,
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National Science Foundation (NSF)
USDOE Office of Science (SC), Basic Energy Sciences (BES)
US Air Force Office of Scientific Research (AFOSR)
AC02-06CH11357; SC0019463; FA9550-17-1-0247; FA9550-14-1-0358; DGE-1324585
ISSN:2041-6520
2041-6539
DOI:10.1039/d0sc03777j