Synthesis and Crystallographic Characterization of a Reduced Bimetallic Yttrium ansa-Metallocene Hydride Complex, [K(crypt)][(μ-CpAn)Y(μ-H)]2 (CpAn = Me2Si[C5H3(SiMe3)-3]2), with a 3.4 Å Yttrium-Yttrium Distance

Justin C. Wedal; Lauren M. Anderson-Sanchez; Megan T. Dumas; Colin A. Gould; María J. Beltrán-Leiva; Cristian Celis-Barros; Dayán Páez-Hernández; Joseph W. Ziller; Jeffrey R. Long; William J. Evans

doi:10.1021/jacs.3c01405

Synthesis and Crystallographic Characterization of a Reduced Bimetallic Yttrium ansa-Metallocene Hydride Complex, [K(crypt)][(μ-Cp^An)Y(μ-H)]₂ (Cp^An = Me₂Si[C₅H₃(SiMe₃)-3]₂), with a 3.4 Å Yttrium-Yttrium Distance

Justin C. Wedal, Lauren M. Anderson-Sanchez, Megan T. Dumas, Colin A. Gould, María J. Beltrán-Leiva, Cristian Celis-Barros, Dayán Páez-Hernández, Joseph W. Ziller, Jeffrey R. Long, William J. Evans

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

8 Scopus citations

Abstract

The reduction of a bimetallic yttrium ansa-metallocene hydride was examined to explore the possible formation of Y-Y bonds with 4d¹ Y(II) ions. The precursor [Cp^AnY(μ-H)(THF)]₂ (Cp^An = Me₂Si[C₅H₃(SiMe₃)-3]₂) was synthesized by hydrogenolysis of the allyl complex Cp^AnY(η³-C₃H₅)(THF), which was prepared from (C₃H₅)MgCl and [Cp^AnY(μ-Cl)]₂. Treatment of [Cp^AnY(μ-H)(THF)]₂ with excess KC₈ in the presence of one equivalent of 2.2.2-cryptand (crypt) generates an intensely colored red-brown product crystallographically identified as [K(crypt)][(μ-Cp^An)Y(μ-H)]₂. The two rings of each Cp^An ligand in the reduced anion [(μ-Cp^An)Y(μ-H)]₂^1- are attached to two yttrium centers in a “flyover” configuration. The 3.3992(6) and 3.4022(7) Å Y···Y distances between the equivalent metal centers within two crystallographically independent complexes are the shortest Y···Y distances observed to date. Ultraviolet-visible (UV-visible)/near infrared (IR) and electron paramagnetic resonance (EPR) spectroscopy support the presence of Y(II), and theoretical analysis describes the singly occupied molecular orbital (SOMO) as an Y-Y bonding orbital composed of metal 4d orbitals mixed with metallocene ligand orbitals. A dysprosium analogue, [K(18-crown-6)(THF)₂][(μ-Cp^An)Dy(μ-H)]₂, was also synthesized, crystallographically characterized, and studied by variable temperature magnetic susceptibility. The magnetic data are best modeled with the presence of one 4f⁹ Dy(III) center and one 4f⁹(5d_z)¹ Dy(II) center with no coupling between them. CASSCF calculations are consistent with magnetic measurements supporting the absence of coupling between the Dy centers.

Original language	English
Pages (from-to)	10730-10742
Number of pages	13
Journal	Journal of the American Chemical Society
Volume	145
Issue number	19
DOIs	https://doi.org/10.1021/jacs.3c01405
State	Published - May 17 2023
Externally published	Yes

Funding

The authors thank the U.S. National Science Foundation for support of this research (CHE-2154255 to W.J.E. and CHE-2102603 to J.R.L.) and FONDECYT 1180017. Furthermore, M.J.B.-L. acknowledges CONICYT/Doctorado Nacional 2015/21151553 for the Ph.D. fellowship. The authors also thank Austin J. Ryan and Daniel N. Huh for help with X-ray crystallography and UC Irvine′s Laser Facility and Professors A. S. Borovik and Jenny Yang for assistance with EPR and IR spectroscopy.

Funders	Funder number
Doctorado
UC Irvine′s Laser Facility
National Science Foundation	CHE-2102603, CHE-2154255
Agencia Nacional de Investigación y Desarrollo
Fondo Nacional de Desarrollo Científico y Tecnológico	1180017

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Wedal, J. C., Anderson-Sanchez, L. M., Dumas, M. T., Gould, C. A., Beltrán-Leiva, M. J., Celis-Barros, C., Páez-Hernández, D., Ziller, J. W., Long, J. R., & Evans, W. J. (2023). Synthesis and Crystallographic Characterization of a Reduced Bimetallic Yttrium ansa-Metallocene Hydride Complex, [K(crypt)][(μ-Cp^An)Y(μ-H)]₂ (Cp^An = Me₂Si[C₅H₃(SiMe₃)-3]₂), with a 3.4 Å Yttrium-Yttrium Distance. Journal of the American Chemical Society, 145(19), 10730-10742. https://doi.org/10.1021/jacs.3c01405

Wedal, Justin C. ; Anderson-Sanchez, Lauren M. ; Dumas, Megan T. et al. / Synthesis and Crystallographic Characterization of a Reduced Bimetallic Yttrium ansa-Metallocene Hydride Complex, [K(crypt)][(μ-Cp^An)Y(μ-H)]₂ (Cp^An = Me₂Si[C₅H₃(SiMe₃)-3]₂), with a 3.4 Å Yttrium-Yttrium Distance. In: Journal of the American Chemical Society. 2023 ; Vol. 145, No. 19. pp. 10730-10742.

@article{42d66640ead444d78e8696a9a55c36fa,

title = "Synthesis and Crystallographic Characterization of a Reduced Bimetallic Yttrium ansa-Metallocene Hydride Complex, [K(crypt)][(μ-CpAn)Y(μ-H)]2 (CpAn = Me2Si[C5H3(SiMe3)-3]2), with a 3.4 {\AA} Yttrium-Yttrium Distance",

abstract = "The reduction of a bimetallic yttrium ansa-metallocene hydride was examined to explore the possible formation of Y-Y bonds with 4d1 Y(II) ions. The precursor [CpAnY(μ-H)(THF)]2 (CpAn = Me2Si[C5H3(SiMe3)-3]2) was synthesized by hydrogenolysis of the allyl complex CpAnY(η3-C3H5)(THF), which was prepared from (C3H5)MgCl and [CpAnY(μ-Cl)]2. Treatment of [CpAnY(μ-H)(THF)]2 with excess KC8 in the presence of one equivalent of 2.2.2-cryptand (crypt) generates an intensely colored red-brown product crystallographically identified as [K(crypt)][(μ-CpAn)Y(μ-H)]2. The two rings of each CpAn ligand in the reduced anion [(μ-CpAn)Y(μ-H)]21- are attached to two yttrium centers in a “flyover” configuration. The 3.3992(6) and 3.4022(7) {\AA} Y···Y distances between the equivalent metal centers within two crystallographically independent complexes are the shortest Y···Y distances observed to date. Ultraviolet-visible (UV-visible)/near infrared (IR) and electron paramagnetic resonance (EPR) spectroscopy support the presence of Y(II), and theoretical analysis describes the singly occupied molecular orbital (SOMO) as an Y-Y bonding orbital composed of metal 4d orbitals mixed with metallocene ligand orbitals. A dysprosium analogue, [K(18-crown-6)(THF)2][(μ-CpAn)Dy(μ-H)]2, was also synthesized, crystallographically characterized, and studied by variable temperature magnetic susceptibility. The magnetic data are best modeled with the presence of one 4f9 Dy(III) center and one 4f9(5dz)1 Dy(II) center with no coupling between them. CASSCF calculations are consistent with magnetic measurements supporting the absence of coupling between the Dy centers.",

author = "Wedal, {Justin C.} and Anderson-Sanchez, {Lauren M.} and Dumas, {Megan T.} and Gould, {Colin A.} and Beltr{\'a}n-Leiva, {Mar{\'i}a J.} and Cristian Celis-Barros and Day{\'a}n P{\'a}ez-Hern{\'a}ndez and Ziller, {Joseph W.} and Long, {Jeffrey R.} and Evans, {William J.}",

note = "Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2023",

month = may,

day = "17",

doi = "10.1021/jacs.3c01405",

language = "English",

volume = "145",

pages = "10730--10742",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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Wedal, JC, Anderson-Sanchez, LM, Dumas, MT, Gould, CA, Beltrán-Leiva, MJ, Celis-Barros, C, Páez-Hernández, D, Ziller, JW, Long, JR & Evans, WJ 2023, 'Synthesis and Crystallographic Characterization of a Reduced Bimetallic Yttrium ansa-Metallocene Hydride Complex, [K(crypt)][(μ-Cp^An)Y(μ-H)]₂ (Cp^An = Me₂Si[C₅H₃(SiMe₃)-3]₂), with a 3.4 Å Yttrium-Yttrium Distance', Journal of the American Chemical Society, vol. 145, no. 19, pp. 10730-10742. https://doi.org/10.1021/jacs.3c01405

Synthesis and Crystallographic Characterization of a Reduced Bimetallic Yttrium ansa-Metallocene Hydride Complex, [K(crypt)][(μ-Cp^An)Y(μ-H)]₂ (Cp^An = Me₂Si[C₅H₃(SiMe₃)-3]₂), with a 3.4 Å Yttrium-Yttrium Distance. / Wedal, Justin C.; Anderson-Sanchez, Lauren M.; Dumas, Megan T. et al.
In: Journal of the American Chemical Society, Vol. 145, No. 19, 17.05.2023, p. 10730-10742.

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

TY - JOUR

T1 - Synthesis and Crystallographic Characterization of a Reduced Bimetallic Yttrium ansa-Metallocene Hydride Complex, [K(crypt)][(μ-CpAn)Y(μ-H)]2 (CpAn = Me2Si[C5H3(SiMe3)-3]2), with a 3.4 Å Yttrium-Yttrium Distance

AU - Wedal, Justin C.

AU - Anderson-Sanchez, Lauren M.

AU - Dumas, Megan T.

AU - Gould, Colin A.

AU - Beltrán-Leiva, María J.

AU - Celis-Barros, Cristian

AU - Páez-Hernández, Dayán

AU - Ziller, Joseph W.

AU - Long, Jeffrey R.

AU - Evans, William J.

PY - 2023/5/17

Y1 - 2023/5/17

N2 - The reduction of a bimetallic yttrium ansa-metallocene hydride was examined to explore the possible formation of Y-Y bonds with 4d1 Y(II) ions. The precursor [CpAnY(μ-H)(THF)]2 (CpAn = Me2Si[C5H3(SiMe3)-3]2) was synthesized by hydrogenolysis of the allyl complex CpAnY(η3-C3H5)(THF), which was prepared from (C3H5)MgCl and [CpAnY(μ-Cl)]2. Treatment of [CpAnY(μ-H)(THF)]2 with excess KC8 in the presence of one equivalent of 2.2.2-cryptand (crypt) generates an intensely colored red-brown product crystallographically identified as [K(crypt)][(μ-CpAn)Y(μ-H)]2. The two rings of each CpAn ligand in the reduced anion [(μ-CpAn)Y(μ-H)]21- are attached to two yttrium centers in a “flyover” configuration. The 3.3992(6) and 3.4022(7) Å Y···Y distances between the equivalent metal centers within two crystallographically independent complexes are the shortest Y···Y distances observed to date. Ultraviolet-visible (UV-visible)/near infrared (IR) and electron paramagnetic resonance (EPR) spectroscopy support the presence of Y(II), and theoretical analysis describes the singly occupied molecular orbital (SOMO) as an Y-Y bonding orbital composed of metal 4d orbitals mixed with metallocene ligand orbitals. A dysprosium analogue, [K(18-crown-6)(THF)2][(μ-CpAn)Dy(μ-H)]2, was also synthesized, crystallographically characterized, and studied by variable temperature magnetic susceptibility. The magnetic data are best modeled with the presence of one 4f9 Dy(III) center and one 4f9(5dz)1 Dy(II) center with no coupling between them. CASSCF calculations are consistent with magnetic measurements supporting the absence of coupling between the Dy centers.

AB - The reduction of a bimetallic yttrium ansa-metallocene hydride was examined to explore the possible formation of Y-Y bonds with 4d1 Y(II) ions. The precursor [CpAnY(μ-H)(THF)]2 (CpAn = Me2Si[C5H3(SiMe3)-3]2) was synthesized by hydrogenolysis of the allyl complex CpAnY(η3-C3H5)(THF), which was prepared from (C3H5)MgCl and [CpAnY(μ-Cl)]2. Treatment of [CpAnY(μ-H)(THF)]2 with excess KC8 in the presence of one equivalent of 2.2.2-cryptand (crypt) generates an intensely colored red-brown product crystallographically identified as [K(crypt)][(μ-CpAn)Y(μ-H)]2. The two rings of each CpAn ligand in the reduced anion [(μ-CpAn)Y(μ-H)]21- are attached to two yttrium centers in a “flyover” configuration. The 3.3992(6) and 3.4022(7) Å Y···Y distances between the equivalent metal centers within two crystallographically independent complexes are the shortest Y···Y distances observed to date. Ultraviolet-visible (UV-visible)/near infrared (IR) and electron paramagnetic resonance (EPR) spectroscopy support the presence of Y(II), and theoretical analysis describes the singly occupied molecular orbital (SOMO) as an Y-Y bonding orbital composed of metal 4d orbitals mixed with metallocene ligand orbitals. A dysprosium analogue, [K(18-crown-6)(THF)2][(μ-CpAn)Dy(μ-H)]2, was also synthesized, crystallographically characterized, and studied by variable temperature magnetic susceptibility. The magnetic data are best modeled with the presence of one 4f9 Dy(III) center and one 4f9(5dz)1 Dy(II) center with no coupling between them. CASSCF calculations are consistent with magnetic measurements supporting the absence of coupling between the Dy centers.

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Wedal JC, Anderson-Sanchez LM, Dumas MT, Gould CA, Beltrán-Leiva MJ, Celis-Barros C et al. Synthesis and Crystallographic Characterization of a Reduced Bimetallic Yttrium ansa-Metallocene Hydride Complex, [K(crypt)][(μ-Cp^An)Y(μ-H)]₂ (Cp^An = Me₂Si[C₅H₃(SiMe₃)-3]₂), with a 3.4 Å Yttrium-Yttrium Distance. Journal of the American Chemical Society. 2023 May 17;145(19):10730-10742. doi: 10.1021/jacs.3c01405