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

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

doi:10.1039/d0sc03777j

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

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

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

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	https://doi.org/10.1039/d0sc03777j
State	Published - Sep 28 2020

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Chemistry(all)

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10.1039/d0sc03777j

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@article{dad41d0c261d415ea3a1d63fc502a4a3,

title = "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.",

author = "Coste, {Scott C.} and Pearson, {Tyler J.} and Altman, {Alison B.} and Klein, {Ryan A.} and Finney, {Brian A.} and Hu, {Michael Y.} and Alp, {E. Ercan} and Bess Vlaisavljevich and Freedman, {Danna E.}",

note = "Funding Information: The aggregate data here allow us to construct a qualitative MO picture (shown in Fig. 6) which describes the M–Sn bonding interaction. A foundational aspect of ligand eld theory towards describing metal–ligand interactions is the introduction of covalency which implies d orbital-based MOs have metal–ligand antibonding character. Indeed, crystallographic, spectroscopic, and theoretical data show that the Sn donor forms a polar-covalent bond in which electron density shis away from Sn with more electronegative transition metals. However, we nd that the 3d-based MOs have no M–Sn antibonding character, countering the classical MO description of coordination complexes. Consequently, the electronic and magnetic properties in 3–6 are more like a free ion description with respect to the M 3d orbitals despite the covalent M–Sn interaction. This is surprising as the Sn 5s/5pz and M 3dz2 orbitals have appropriate symmetry and orbital overlap to form a bonding interaction. We posit that the origin for this observation is energetic mismatch between the M 3d orbitals and the electropositive Sn donor orbitals. The Hirshfeld charge decomposition analysis supports this as the higher lying M 4s, 4p, and 4d orbitals have more atomic Sn contribution than the 3d-based MOs. This suggests that the localization of the M 3d orbitals are due to the higher energy of the Ph3Sn donor orbitals relative to the 3d orbitals. This energetic mismatch is supported by atomic ionization potentials and energies of the hydrogen-like atomic orbitals.55 Publisher Copyright: {\textcopyright} 2020 The Royal Society of Chemistry.",

year = "2020",

month = sep,

day = "28",

doi = "10.1039/d0sc03777j",

language = "English (US)",

volume = "11",

pages = "9971--9977",

journal = "Chemical Science",

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publisher = "Royal Society of Chemistry",

number = "36",

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TY - JOUR

T1 - Orbital energy mismatch engenders high-spin ground states in heterobimetallic complexes

AU - Coste, Scott C.

AU - Pearson, Tyler J.

AU - Altman, Alison B.

AU - Klein, Ryan A.

AU - Finney, Brian A.

AU - Hu, Michael Y.

AU - Alp, E. Ercan

AU - Vlaisavljevich, Bess

AU - Freedman, Danna E.

N1 - Funding Information: The aggregate data here allow us to construct a qualitative MO picture (shown in Fig. 6) which describes the M–Sn bonding interaction. A foundational aspect of ligand eld theory towards describing metal–ligand interactions is the introduction of covalency which implies d orbital-based MOs have metal–ligand antibonding character. Indeed, crystallographic, spectroscopic, and theoretical data show that the Sn donor forms a polar-covalent bond in which electron density shis away from Sn with more electronegative transition metals. However, we nd that the 3d-based MOs have no M–Sn antibonding character, countering the classical MO description of coordination complexes. Consequently, the electronic and magnetic properties in 3–6 are more like a free ion description with respect to the M 3d orbitals despite the covalent M–Sn interaction. This is surprising as the Sn 5s/5pz and M 3dz2 orbitals have appropriate symmetry and orbital overlap to form a bonding interaction. We posit that the origin for this observation is energetic mismatch between the M 3d orbitals and the electropositive Sn donor orbitals. The Hirshfeld charge decomposition analysis supports this as the higher lying M 4s, 4p, and 4d orbitals have more atomic Sn contribution than the 3d-based MOs. This suggests that the localization of the M 3d orbitals are due to the higher energy of the Ph3Sn donor orbitals relative to the 3d orbitals. This energetic mismatch is supported by atomic ionization potentials and energies of the hydrogen-like atomic orbitals.55 Publisher Copyright: © 2020 The Royal Society of Chemistry.

PY - 2020/9/28

Y1 - 2020/9/28

N2 - 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.

AB - 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.

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UR - http://www.scopus.com/inward/citedby.url?scp=85090948856&partnerID=8YFLogxK

U2 - 10.1039/d0sc03777j

DO - 10.1039/d0sc03777j

M3 - Article

C2 - 34094259

AN - SCOPUS:85090948856

SN - 2041-6520

VL - 11

SP - 9971

EP - 9977

JO - Chemical Science

JF - Chemical Science

IS - 36

ER -

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

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CCDC 2015381: Experimental Crystal Structure Determination

CCDC 2015379: Experimental Crystal Structure Determination

CCDC 2015383: Experimental Crystal Structure Determination

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

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CCDC 2015381: Experimental Crystal Structure Determination

CCDC 2015379: Experimental Crystal Structure Determination

CCDC 2015383: Experimental Crystal Structure Determination

Cite this