ACS Publications. Most Trusted. Most Cited. Most Read
Europium(II) and Ytterbium(II) Cyclic Organohydroborates with Agostic Interactions

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2005, 44, 17, 6052-6061
    Article

    Europium(II) and Ytterbium(II) Cyclic Organohydroborates with Agostic Interactions
    Click to copy article linkArticle link copied!

    View Author Information
    Department of Chemistry, The Ohio State University, Columbus, Ohio 43210
    Other Access OptionsSupporting Information (2)

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2005, 44, 17, 6052–6061
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ic050573i
    Published July 22, 2005
    Copyright © 2005 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    The divalent lanthanide bis((cyclooctane-1,5-diyl)dihydroborate) complexes {K(THF)4}2{Ln{(μ-H)2BC8H14}4} (Ln = Eu, 3; Yb, 4) were prepared by a metathesis reaction between (THF)xLnCl2 and K[H2BC8H14] in THF in a 1:4 molar ratio. Although the reaction ratios were varied between 1:3 and 1:6, complexes 3 and 4 were the only lanthanide 9-BBN hydroborates produced. Because of disorder of THF in crystals of 3 and 4, good single-crystal X-ray structural data could not be obtained. However, when the potassium cation was replaced by the tetramethylammonium cation or when MeTHF (2-methyltetrahydrofuran) was employed in place of THF, good quality crystals were obtained. Complexes [NMe4]2[Ln{(μ-H)2BC8H14}4] (Ln = Eu, 5; Yb, 6) were afforded by metathesis reactions of NMe4Cl with 3 and 4 in situ. On the basis of the single-crystal X-ray diffraction analysis, the four 9-BBN tetrahydroborate ligands are tetrahedrally arranged around the lanthanide cation in 5 and 6. The two structures differ in that one α-C−H bond from each of the four {(μ-H)2BC8H14}4 units exhibits an agostic interaction with Eu(II) in 5 but, in complex 6, only two of the α-C−H bonds form agostic interactions with Yb(II). Complexes {K(MeTHF)3}2{Ln{(μ-H)2BC8H14}4} (Ln = Eu, 7; Yb, 8) were produced by employing MeTHF in place of THF. The structures of 7 and 8 display connectivity between the anion {Ln{(μ-H)2BC8H14}4}2- and the cation {K(MeTHF)3}+, in which the potassium not only interacts directly with the hydrogens of the Ln−H−B bridged bonds but is also involved in agostic interactions with α-C−H bonds. By systematically examining the structures of complexes 3−8 and taking into account the previously reported complexes (THF)4Ln{(μ-H)2BC8H14}2 (Ln = Eu, 1; Yb, 2), it is concluded that Eu(II) appears to have a better ability to form agostic interactions than Yb(II) because of its larger size, even though Yb(II) has a higher positive charge density.

    Copyright © 2005 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    *

     To whom correspondance should be addressed. E-mail:  shore@ chemistry.ohio-state.edu.

    Supporting Information Available

    Click to copy section linkSection link copied!

    Six X-ray crystallographic files in CIF format and molecular structures and IR spectra of complexes 3−8 in pdf format. This material is available free of charge via the Internet at http://pubs.acs.org.

    Terms & Conditions

    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

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 23 publications.

    1. Chengkun Yi, Ziyi Xu, Liang Chen, Wenshan Ren. Cerocene and Lanthanocene Chalcogenides: Synthesis, Structure, and Luminescence. Inorganic Chemistry 2022, 61 (13) , 5373-5379. https://doi.org/10.1021/acs.inorgchem.2c00212
    2. Christopher M. Bateman, Hailey Beal, Joshua E. Barker, Brena L. Thompson, Drake Donovan, Bradley J. Grant, Jesse Shooter, Jordan H. Arakawa, Spencer Johnson, Caleb J. Allen, James L. Yates, Ryota Kato, Colby W. K. Tinsley, Lev. N. Zakharov, Eric R. Abbey. One-Step Conversion of Potassium Organotrifluoroborates to Metal Organoborohydrides. Organic Letters 2018, 20 (13) , 3784-3787. https://doi.org/10.1021/acs.orglett.8b01373
    3. Gabriela Marinescu, Catalin Maxim, Rodolphe Clérac, and Marius Andruh . [RuIII(valen)(CN)2]−: a New Building Block To Design 4d–4f Heterometallic Complexes. Inorganic Chemistry 2015, 54 (12) , 5621-5623. https://doi.org/10.1021/acs.inorgchem.5b00889
    4. Gary L. Guillet, Jesse B. Gordon, Gianna N. Di Francesco, Matthew W. Calkins, Erik Čižmár, Khalil A. Abboud, Mark W. Meisel, Ricardo García-Serres, and Leslie J. Murray . A Family of Tri- and Dimetallic Pyridine Dicarboxamide Cryptates: Unusual O,N,O-Coordination and Facile Access to Secondary Coordination Sphere Hydrogen Bonding Interactions. Inorganic Chemistry 2015, 54 (6) , 2691-2704. https://doi.org/10.1021/ic502873d
    5. Scott R. Daly and Gregory S. Girolami. Synthesis, Characterization, and Structures of Divalent Europium and Ytterbium N,N-Dimethylaminodiboranates. Inorganic Chemistry 2010, 49 (10) , 4578-4585. https://doi.org/10.1021/ic100292u
    6. Anthony G. M. Barrett,, Mark R. Crimmin,, Michael S. Hill,, Peter B. Hitchcock, and, Panayiotis A. Procopiou. Reactions of β-Diketiminate-Stabilized Calcium Amides with 9-Borabicyclo[3.3.1]nonane (9-BBN). Organometallics 2007, 26 (16) , 4076-4079. https://doi.org/10.1021/om070083t
    7. Roberto M. Diaz-Rodriguez, Alexandros A. Kitos, Muralee Murugesu. Expanding the series of alkali metal plumbolyl complexes to Na and K. Dalton Transactions 2022, 51 (38) , 14420-14428. https://doi.org/10.1039/D2DT02615E
    8. Johannes Kretsch, Anne‐Kathrin Kreyenschmidt, Timo Schillmöller, Märt Lõkov, Regine Herbst‐Irmer, Ivo Leito, Dietmar Stalke. Bis(4‐benzhydryl‐benzoxazol‐2‐yl)methane – from a Bulky NacNac Alternative to a Trianion in Alkali Metal Complexes. Chemistry – A European Journal 2021, 27 (38) , 9858-9865. https://doi.org/10.1002/chem.202100616
    9. D. M. Lyubov, I. V. Basalov, A. S. Shavyrin, A. V. Cherkasov, A. A. Trifonov. Cleavage of B−C bonds and Anion [PhBH3]− Formation in the Reaction of the Yb(II) Hydride Complex with BPh3. Russian Journal of Coordination Chemistry 2019, 45 (10) , 728-733. https://doi.org/10.1134/S1070328419100026
    10. Ryo Tanaka, Yuto Shinto, Ryusei Matsuzaki, Yuushou Nakayama, Takeshi Shiono. Stereospecific polymerization of conjugated dienes using neodymium alkylborohydride complexes. Dalton Transactions 2019, 48 (21) , 7267-7273. https://doi.org/10.1039/C8DT04220A
    11. Thomas Behrsing, Glen B. Deacon, Peter C. Junk. Element 70 – Ytterbium. Australian Journal of Chemistry 2019, 72 (12) , 927. https://doi.org/10.1071/CH19527
    12. Min Zhang, Zhenhua Liang, Jun Ling, Xufeng Ni, Zhiquan Shen. Carbon bridged triphenolate lanthanide complexes: synthesis, characterization, DFT studies and catalytic activities for isoprene polymerization. Dalton Transactions 2015, 44 (24) , 11182-11190. https://doi.org/10.1039/C5DT01241D
    13. Crispin Lichtenberg, Thomas P. Spaniol, Lionel Perrin, Laurent Maron, Jun Okuda. Reversible 1,4‐Insertion of Pyridine Into a Highly Polar Metal–Carbon Bond: Effect of the Second Metal. Chemistry – A European Journal 2012, 18 (21) , 6448-6452. https://doi.org/10.1002/chem.201200808
    14. Sung-In Ha, Min-Ah Song, Dae-Young Park, An-Soo Kang, Sang-Bong Moon, Jang-Hoon Chung. Synthesis and Structural Characterization of Novel Anionic Thulium(III) Cyclic Organohydroborate Complex with Agostic Interactions {K(η 6 -C 6 H 5 Me) 2 }{Tm[(μ-H) 2 (BC 8 H 14 )] 4 }. Bulletin of the Korean Chemical Society 2011, 32 (10) , 3790-3792. https://doi.org/10.5012/bkcs.2011.32.10.3790
    15. Anthony S. R. Chesman, David R. Turner, Glen B. Deacon, Stuart R. Batten. New Approaches to 12‐Coordination: Structural Consequences of Steric Stress, Lanthanoid Contraction and Hydrogen Bonding. European Journal of Inorganic Chemistry 2010, 2010 (18) , 2798-2812. https://doi.org/10.1002/ejic.201000257
    16. Keith Izod, William Clegg, Ross W. Harrington. Lanthanide(ii) complexes of a phosphine-borane-stabilised carbanion. Dalton Transactions 2010, 39 (29) , 6705. https://doi.org/10.1039/c001468k
    17. Kristen Aznavour, Muhammed Yousufuddin, Robert Bau, Garry J. McIntyre, Sax A. Mason, Xuenian Chen, Soyoung Lim, Christine E. Pleĉnik, Shengming Liu, Bin Du, Edward A. Meyers, Sheldon G. Shore. A neutron diffraction study of ytterbium(II) cyclic organohydroborates. Journal of Molecular Structure 2008, 890 (1-3) , 277-280. https://doi.org/10.1016/j.molstruc.2008.04.006
    18. Xuenian Chen, Shengming Liu, Bin Du, Edward A. Meyers, Sheldon G. Shore. The Structure of Potassium and Tetramethylammonium Salts of the Cyclic Organohydroborate Anion [H 2 BC 8 H 14 ] – with Different Solvent Ligands. European Journal of Inorganic Chemistry 2007, 2007 (35) , 5563-5570. https://doi.org/10.1002/ejic.200700836
    19. Jan Spielmann, Sjoerd Harder. Hydrocarbon‐Soluble Calcium Hydride: A “Worker‐Bee” in Calcium Chemistry. Chemistry – A European Journal 2007, 13 (32) , 8928-8938. https://doi.org/10.1002/chem.200701028
    20. Dennis Heitmann, Cameron Jones, Peter C. Junk, Kai-Alexander Lippert, Andreas Stasch. Homoleptic lanthanide( ii )–bis(guanidinate) complexes, [Ln(Giso) 2 ] (Giso = [(ArN) 2 CN(C 6 H 11 ) 2 ] − , Ar = C 6 H 3 Pr i 2 -2,6): planar 4-coordinate (Ln = Sm or Eu) vs distorted tetrahedral (Ln = Yb) geometries. Dalton Trans. 2007, 102 (2) , 187-189. https://doi.org/10.1039/B614028A
    21. William J. Evans, Sara E. Lorenz, Joseph W. Ziller. Yttrium metallocene borane chemistry: isolation of 9-BBN substitution and coordination complexes in a single crystal, {(C5Me5)2Y[η3-C3H4(BC8H14)]} and {(C5Me5)2Y(µ-H)2BC8H14}. Chemical Communications 2007, 204 (44) , 4662. https://doi.org/10.1039/b709841c
    22. Mathieu Roger, Noémi Barros, Thérèse Arliguie, Pierre Thuéry, Laurent Maron, Michel Ephritikhine. U(SMes*) n , ( n = 3, 4) and Ln(SMes*) 3 (Ln = La, Ce, Pr, Nd):  Lanthanide(III)/Actinide(III) Differentiation in Agostic Interactions and an Unprecedented η 3 Ligation Mode of the Arylthiolate Ligand, from X-ray Diffraction and DFT Analysis. Journal of the American Chemical Society 2006, 128 (27) , 8790-8802. https://doi.org/10.1021/ja0584830
    23. A. L. Johnson. Boron. Annual Reports Section "A" (Inorganic Chemistry) 2006, 102 , 59. https://doi.org/10.1039/b508354k
    Download PDF
    Go to Inorganic Chemistry
    Get e-Alerts
    Get e-Alerts

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2005, 44, 17, 6052–6061
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ic050573i
    Published July 22, 2005
    Copyright © 2005 American Chemical Society
    Request reuse permissions

    Article Views

    517

    Altmetric

    -

    Citations

    23
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.