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Synthetic, Structural, and Spectroscopic Characterization of a Novel Family of High-Spin Iron(II) [(β-Diketiminate)(phosphanylphosphido)] Complexes
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    Synthetic, Structural, and Spectroscopic Characterization of a Novel Family of High-Spin Iron(II) [(β-Diketiminate)(phosphanylphosphido)] Complexes
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    Department of Inorganic Chemistry, Chemical Faculty, Gdańsk University of Technology, G. Narutowicza St. 11/12, Gdańsk PL-80-233, Poland
    Department of General and Coordination Chemistry, Faculty of Chemistry, Maria Curie-Skłodowska University, Maria Curie-Skłodowska Sq. 2, Lublin PL-20-031, Poland
    § Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States
    National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, United States
    Department of Chemistry, University of Idaho, Moscow, Idaho 83844, United States
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2017, 56, 18, 11030–11042
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    https://doi.org/10.1021/acs.inorgchem.7b01374
    Published August 25, 2017
    Copyright © 2017 American Chemical Society

    Abstract

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    This work describes a series of iron(II) phosphanylphosphido complexes. These compounds were obtained by reacting lithiated diphosphanes R2PP(SiMe3)Li (R = t-Bu, i-Pr) with an iron(II) β-diketiminate complex, [LFe(μ2-Cl)2Li(DME)2] (1), where DME = 1,2-dimethoxyethane and L = Dippnacnac (β-diketiminate). While the reaction of 1 with t-Bu2PP(SiMe3)Li yields [LFe(η1-Me3SiPP-t-Bu2)] (2), that of 1 with equimolar amounts of i-Pr2PP(SiMe3)Li, in DME, leads to [LFe(η2-i-Pr2PPSiMe3)] (3). In contrast, the reaction of 1 with (i-Pr2N)2PP(SiMe3)Li provides not an iron-containing complex but 1-[(diisopropylamino)phosphine]-2,4-bis(diisopropylamino)-3-(trimethylsilyl)tetraphosphetane (4). The structures of 24 were determined using diffractometry. Thus, 2 exhibits a three-coordinate iron site and 3 a four-coordinate iron site. The increase in the coordination number is induced by the change from an anticlinal to a synclinal conformation of the phoshpanylphosphido ligands. The electronic structures of 2 and 3 were assessed through a combined field-dependent 57Fe Mössbauer and high-frequency and -field electron paramagnetic resonance spectroscopic investigation in conjunction with analysis of their magnetic susceptibility and magnetization data. These studies revealed two high-spin iron(II) sites with S = 2 ground states that have different properties. While 2 exhibits a zero-field splitting described by a positive D parameter (D = +17.4 cm–1; E/D = 0.11) for 3, this parameter is negative [D = −25(5) cm–1; E/D = 0.15(5)]. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations provide insights into the origin of these differences and allow us to rationalize the fine and hyperfine structure parameters of 2 and 3. Thus, for 2, the spin–orbit coupling mixes a z2-type ground state with two low-lying {xz/yz} orbital states. These interactions lead to an easy plane of magnetization, which is essentially parallel to the plane defined by the N–Fe–N atoms. For 3, we find a yz-type ground state that is strongly mixed with a low-lying z2-type orbital state. In this case, the spin–orbit interaction leads to a partial unquenching of the orbital momentum along the x axis, that is, to an easy axis of magnetization oriented roughly along the Fe–P bond of the phosphido moiety.

    Copyright © 2017 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b01374.

    • Crystallographic details, magnetic susceptibility and reduced magnetization measurements, 57Fe Mossbauer spectroscopy, energy-level diagrams and spin expectation values, 1H NMR spectroscopic data, and DFT results (PDF)

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    CCDC 10535781053580 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

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    This article is cited by 12 publications.

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    2. A. Ziółkowska, N. Szynkiewicz, J. Pikies, Ł. Ponikiewski. Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu2P–P(SiMe3) Ligand. Inorganic Chemistry 2020, 59 (16) , 11305-11315. https://doi.org/10.1021/acs.inorgchem.0c00824
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    7. Aleksandra Ziółkowska, Natalia Szynkiewicz, Jerzy Pikies, Łukasz Ponikiewski. Reactivity study of a β-diketiminate titanium(III) complex with a phosphanylphosphido ligand towards chlorophosphanes. A new method of synthesis of β-diketiminate titanium(IV) complexes with versatile phosphanylphosphinidenes. Polyhedron 2019, 169 , 278-286. https://doi.org/10.1016/j.poly.2019.04.051
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    9. Huifen Pan, Yafei Li, Yalan Wang, Yu Ge, Shengwang Xia, Yahong Li. A series of aluminium complexes based on a β-diketiminate ligand: Synthesis, structures and their application to ring-opening polymerization of ε-caprolactone. Polyhedron 2019, 166 , 210-216. https://doi.org/10.1016/j.poly.2019.03.054
    10. Natalia Szynkiewicz, Łukasz Ponikiewski, Rafał Grubba. Diphosphination of CO 2 and CS 2 mediated by frustrated Lewis pairs – catalytic route to phosphanyl derivatives of formic and dithioformic acid. Chemical Communications 2019, 55 (20) , 2928-2931. https://doi.org/10.1039/C9CC00621D
    11. Kinga Kaniewska, Alina Dragulescu‐Andrasi, Łukasz Ponikiewski, Jerzy Pikies, Sebastian A. Stoian, Rafał Grubba. Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand. European Journal of Inorganic Chemistry 2018, 2018 (38) , 4298-4308. https://doi.org/10.1002/ejic.201800850
    12. Aleksandra Ziółkowska, Natalia Szynkiewicz, Aleksandra Wiśniewska, Jerzy Pikies, Łukasz Ponikiewski. Reactions of (Ph) t BuP-P(SiMe 3 )Li·3THF with [(PNP)TiCl 2 ] and [ Me NacNacTiCl 2 ·THF]: synthesis of first PNP titanium( iv ) complex with the phosphanylphosphinidene ligand [(PNP)Ti(Cl){η 2 -P-P(Ph) t Bu}]. Dalton Transactions 2018, 47 (29) , 9733-9741. https://doi.org/10.1039/C8DT01833B

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2017, 56, 18, 11030–11042
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.7b01374
    Published August 25, 2017
    Copyright © 2017 American Chemical Society

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