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Title: Synthesis and characterization of 2-hydroxy-pyridine modified Group 4 alkoxides

Abstract

Here, the reaction of Group 4 metal alkoxides ([M(OR) 4]) with the potentially bidentate ligand, 2-hydroxy-pyridine (2-HO-(NC 5H 4) or H-PyO), led to the isolation of a family of compounds. The products isolated from the reaction of [M(OR) 4] [where M = Ti, Zr, or Hf; OR = OPri (OCH(CH 3) 2), OBut (OC(CH3)3), or ONep (OCH2C(CH3)3] under a variety of stoichiometries with H-PyO were identified by single crystal X-ray diffraction as [(OPr i) 2(PyO-κ 2(O,N))Ti(μ-OPr i)] 2, [(ONep) 2Ti(μ(O)-PyO-κ 2(O,N)) 2(μ-ONep)Ti(ONep)3], [(ONep) 2Ti(μ(O)-PyO-κ 2(O,N))(η 1(N),μ(O)-PyO)(μ-O)Ti(ONep) 2] 2, [H][(PyO-κ 2(O,N))(η 1(O)-PyO)Ti(ONep) 3], [(OR) 2Zr(μ(O)-PyO-κ 2(O,N)) 2(μ-OR)Zr(OR) 3] (OR = OBu t, ONep), [(OR) 2Zr(μ(O,N)-PyO-κ 2(O,N)) 2(μ(O,N)-PyO)Zr(OR) 3] (OR = OBu t, ONep), [[(OBu t) 2Zr(μ(O)-PyO-(κ 2(N,O))(μ(O,N)-PyO) 2Zr(OBut)](μ 3-O)] 2, [[(ONep)(PyO-κ 2(N,O))Zr(μ(O,N)-PyO-κ 2(N,O)) 2(μ(O)-PyO-κ2(N,O))Zr(ONep)](μ3-O)] 2, [(OBut)(PyO-κ 2(O,N))Zr(μ(O)-PyO-κ 2(O,N)) 2((μ(O,N)-PyO)Zr(OBu t) 3], [(OBu t)2Hf(μ(O)-PyO-κ 2(N,O)) 2(μ-OBut)Hf(OBut) 3], [(OR) 2 M(μ(O)-PyO-κ 2(N,O)) 2(μ(O,N)-PyO)M(OR) 3] (OR = OBu t, ONep), and [(ONep) 3Hf(μ-ONep)(η 1(N),μ(O)-PyO)] 2Hf(ONep) 2·tol. The structural diversity of the binding modes of the PyO led to a number of novel structure types in comparison to other pyridine alkoxy derivatives. The majority of compounds adopt a dinuclear arrangement but oxo-based tetra-, tri-, and monomers were observed as well. Compounds 1–12 were further characterizedmore » using a variety of analytical techniques including Fourier Transform Infrared Spectroscopy, elemental analysis, and multinuclear NMR spectroscopy.« less

Authors:
 [1];  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1339287
Report Number(s):
SAND-2015-11104J
Journal ID: ISSN 0095-8972; 617405
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Coordination Chemistry
Additional Journal Information:
Journal Volume: 69; Journal Issue: 9; Journal ID: ISSN 0095-8972
Publisher:
Taylor & Francis
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alkoxide; 2-hydroxy pyridine; titanium; zirconium; hafnium

Citation Formats

Boyle, Timothy J., and Sivonxay, Eric. Synthesis and characterization of 2-hydroxy-pyridine modified Group 4 alkoxides. United States: N. p., 2016. Web. doi:10.1080/00958972.2016.1183253.
Boyle, Timothy J., & Sivonxay, Eric. Synthesis and characterization of 2-hydroxy-pyridine modified Group 4 alkoxides. United States. doi:10.1080/00958972.2016.1183253.
Boyle, Timothy J., and Sivonxay, Eric. Thu . "Synthesis and characterization of 2-hydroxy-pyridine modified Group 4 alkoxides". United States. doi:10.1080/00958972.2016.1183253. https://www.osti.gov/servlets/purl/1339287.
@article{osti_1339287,
title = {Synthesis and characterization of 2-hydroxy-pyridine modified Group 4 alkoxides},
author = {Boyle, Timothy J. and Sivonxay, Eric},
abstractNote = {Here, the reaction of Group 4 metal alkoxides ([M(OR)4]) with the potentially bidentate ligand, 2-hydroxy-pyridine (2-HO-(NC5H4) or H-PyO), led to the isolation of a family of compounds. The products isolated from the reaction of [M(OR)4] [where M = Ti, Zr, or Hf; OR = OPri (OCH(CH3)2), OBut (OC(CH3)3), or ONep (OCH2C(CH3)3] under a variety of stoichiometries with H-PyO were identified by single crystal X-ray diffraction as [(OPri)2(PyO-κ2(O,N))Ti(μ-OPri)]2, [(ONep)2Ti(μ(O)-PyO-κ2(O,N))2(μ-ONep)Ti(ONep)3], [(ONep)2Ti(μ(O)-PyO-κ2(O,N))(η1(N),μ(O)-PyO)(μ-O)Ti(ONep)2]2, [H][(PyO-κ2(O,N))(η1(O)-PyO)Ti(ONep)3], [(OR)2Zr(μ(O)-PyO-κ2(O,N))2(μ-OR)Zr(OR)3] (OR = OBut, ONep), [(OR)2Zr(μ(O,N)-PyO-κ2(O,N))2(μ(O,N)-PyO)Zr(OR)3] (OR = OBut, ONep), [[(OBut)2Zr(μ(O)-PyO-(κ2(N,O))(μ(O,N)-PyO)2Zr(OBut)](μ3-O)]2, [[(ONep)(PyO-κ2(N,O))Zr(μ(O,N)-PyO-κ2(N,O))2(μ(O)-PyO-κ2(N,O))Zr(ONep)](μ3-O)]2, [(OBut)(PyO-κ2(O,N))Zr(μ(O)-PyO-κ2(O,N))2((μ(O,N)-PyO)Zr(OBut)3], [(OBut)2Hf(μ(O)-PyO-κ2(N,O))2(μ-OBut)Hf(OBut)3], [(OR)2 M(μ(O)-PyO-κ2(N,O))2(μ(O,N)-PyO)M(OR)3] (OR = OBut, ONep), and [(ONep)3Hf(μ-ONep)(η1(N),μ(O)-PyO)]2Hf(ONep)2·tol. The structural diversity of the binding modes of the PyO led to a number of novel structure types in comparison to other pyridine alkoxy derivatives. The majority of compounds adopt a dinuclear arrangement but oxo-based tetra-, tri-, and monomers were observed as well. Compounds 1–12 were further characterized using a variety of analytical techniques including Fourier Transform Infrared Spectroscopy, elemental analysis, and multinuclear NMR spectroscopy.},
doi = {10.1080/00958972.2016.1183253},
journal = {Journal of Coordination Chemistry},
issn = {0095-8972},
number = 9,
volume = 69,
place = {United States},
year = {2016},
month = {5}
}

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Works referenced in this record:

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Structurally characterized group 4 metal alkoxides modified with the pyridyl-based ligands 2-mercapto pyridine n-oxide and 3,3′-dihydroxy-2,2′-bipyridine
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4,6-Dihydroxypyrimidine: a selective bridging ligand for controlled Group IV metal alkoxide structures
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Heterobimetallic platinum-titanium complexes: potential anticancer drugs
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Controlled Synthesis of a Structurally Characterized Family of Sterically Constrained Heterocyclic Alkoxy-Modified Titanium Alkoxides
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Titanium pyridonates and amidates: novel catalysts for the synthesis of random copolymers
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Titanium pyridonates for the homo- and copolymerization of rac-lactide and ε-caprolactone
journal, January 2015

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  • Dalton Transactions, Vol. 44, Issue 27
  • DOI: 10.1039/C5DT01162K

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Unusual structurally characterized pyridine carbinoxide copper(II) coordination compounds, isolated from organic solvents
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Coordination chemistry of 2,6-dimethanol pyridine with early transition metal alkoxide compounds
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Precursor Structural Influences on the Final ZnO Nanoparticle Morphology from a Novel Family of Structurally Characterized Zinc Alkoxy Alkyl Precursors
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Series of Comparable Dinuclear Group 4 Neo-pentoxide Precursors for Production of pH Dependent Group 4 Nanoceramic Morphologies
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    Works referencing / citing this record:

    Structurally characterized group 4 metal alkoxides modified with the pyridyl-based ligands 2-mercapto pyridine n-oxide and 3,3′-dihydroxy-2,2′-bipyridine
    journal, September 2008


    A Novel Family of Structurally Characterized Lithium Cobalt Double Aryloxides and the Nanoparticles and Thin Films Generated Therefrom
    journal, October 2003

    • Boyle, Timothy J.; Rodriguez, Mark A.; Ingersoll, David
    • Chemistry of Materials, Vol. 15, Issue 20
    • DOI: 10.1021/cm020902u

    Precursor Structural Influences on the Final ZnO Nanoparticle Morphology from a Novel Family of Structurally Characterized Zinc Alkoxy Alkyl Precursors
    journal, August 2004

    • Boyle, Timothy J.; Bunge, Scott D.; Andrews, Nicholas L.
    • Chemistry of Materials, Vol. 16, Issue 17
    • DOI: 10.1021/cm0493997

    Chemical aspects of solution routes to perovskite-phase mixed-metal oxides from metal-organic precursors
    journal, May 1993

    • Chandler, Clive D.; Roger, Christophe.; Hampden-Smith, Mark J.
    • Chemical Reviews, Vol. 93, Issue 3
    • DOI: 10.1021/cr00019a015

    Synthesis, structural principles and reactivity of heterometallic alkoxides
    journal, September 1990

    • Caulton, Kenneth G.; Hubert-Pfalzgraf, Liliane G.
    • Chemical Reviews, Vol. 90, Issue 6
    • DOI: 10.1021/cr00104a003

    Heterobimetallic platinum-titanium complexes: potential anticancer drugs
    journal, June 1993

    • Berardini, M.; Emge, T. J.; Brennan, J. G.
    • Inorganic Chemistry, Vol. 32, Issue 12
    • DOI: 10.1021/ic00064a024

    Cadmium Amido Alkoxide and Alkoxide Precursors for the Synthesis of Nanocrystalline CdE (E = S, Se, Te)
    journal, March 2005

    • Boyle, Timothy J.; Bunge, Scott D.; Alam, Todd M.
    • Inorganic Chemistry, Vol. 44, Issue 5
    • DOI: 10.1021/ic0485155

    Controlled Synthesis of a Structurally Characterized Family of Sterically Constrained Heterocyclic Alkoxy-Modified Titanium Alkoxides
    journal, March 2007

    • Boyle, Timothy J.; Sewell, Robin M.; Ottley, Leigh Anna M.
    • Inorganic Chemistry, Vol. 46, Issue 5
    • DOI: 10.1021/ic0618798

    Series of Comparable Dinuclear Group 4 Neo-pentoxide Precursors for Production of pH Dependent Group 4 Nanoceramic Morphologies
    journal, December 2010

    • Boyle, Timothy J.; Ottley, Leigh Anna M.; Hoppe, Sarah M.
    • Inorganic Chemistry, Vol. 49, Issue 23
    • DOI: 10.1021/ic101205d

    Synthesis and Structural Characterization of a Family of Modified Hafnium tert -Butoxide for Use as Precursors to Hafnia Nanoparticles
    journal, November 2012

    • Boyle, Timothy J.; Steele, Leigh Anna M.; Burton, Patrick D.
    • Inorganic Chemistry, Vol. 51, Issue 22
    • DOI: 10.1021/ic300622h

    Titanium(IV) Neopentoxides. X-ray Structures of Ti 33 -O)(μ 3 -Cl)(μ-OCH 2 CMe 3 ) 3 (OCH 2 CMe 3 ) 6 and [Ti(μ-OCH 2 CMe 3 )(OCH 2 CMe 3 ) 3 ] 2
    journal, July 1997

    • Boyle, Timothy J.; Alam, Todd M.; Mechenbier, Eric R.
    • Inorganic Chemistry, Vol. 36, Issue 15
    • DOI: 10.1021/ic960924g

    Titanium(IV) Neopentoxides. X-ray Structures of Ti 33 -O)(μ 3 -Cl)-(μ-OCH 2 CMe 3 ) 3 (OCH 2 CMe 3 ) 6 and [Ti(μ-OCH 2 CMe 3 )-(OCH 2 CMe 3 ) 3 ] 2
    journal, December 1997

    • Boyle, Timothy J.; Alam, Todd M.; Mechenbier, Eric R.
    • Inorganic Chemistry, Vol. 36, Issue 27
    • DOI: 10.1021/ic971335t

    Homo- and hetero-metallic rhenium oxomethoxide complexes with a M4(µ-O)2(µ-OMe)4 planar core—a new family of metal alkoxides displaying a peculiar structural disorder. Preparation and X-ray single crystal study
    journal, January 2001

    • Seisenbaeva, Gulaim A.; Shevelkov, Andrei V.; Tegenfeldt, Jörgen
    • Journal of the Chemical Society, Dalton Transactions, Issue 19
    • DOI: 10.1039/b103287a

    4,6-Dihydroxypyrimidine: a selective bridging ligand for controlled Group IV metal alkoxide structures
    journal, January 2003

    • Boyle, Timothy J.; Rodriguez, Mark A.; Alam, Todd M.
    • Dalton Transactions, Issue 24
    • DOI: 10.1039/b310087a

    Zirconium bis(pyridonate): a modified amidate complex for enhanced substrate scope in aminoalkene cyclohydroamination
    journal, January 2010

    • Bexrud, Jason A.; Schafer, Laurel L.
    • Dalton Trans., Vol. 39, Issue 2
    • DOI: 10.1039/b913393c

    Titanium pyridonates and amidates: novel catalysts for the synthesis of random copolymers
    journal, January 2013

    • Webster, Ruth L.; Noroozi, Nazbanoo; Hatzikiriakos, Savvas G.
    • Chem. Commun., Vol. 49, Issue 1
    • DOI: 10.1039/c2cc37201k

    Titanium pyridonates for the homo- and copolymerization of rac-lactide and ε-caprolactone
    journal, January 2015

    • Gilmour, Damon J.; Webster, Ruth L.; Perry, Mitchell R.
    • Dalton Transactions, Vol. 44, Issue 27
    • DOI: 10.1039/c5dt01162k

    Unusual structurally characterized pyridine carbinoxide copper(II) coordination compounds, isolated from organic solvents
    journal, February 2010

    • Boyle, Timothy J.; Ottley, leighanna M.; Raymond, Rebecca
    • Journal of Coordination Chemistry, Vol. 63, Issue 4
    • DOI: 10.1080/00958970903556088

    Coordination chemistry of 2,6-dimethanol pyridine with early transition metal alkoxide compounds
    journal, March 2015

    • Boyle, Timothy J.; Neville, Michael L.; Yonemoto, Daniel T.
    • Journal of Coordination Chemistry, Vol. 68, Issue 9
    • DOI: 10.1080/00958972.2015.1028382

    An Investigation of Group (IV) Alkoxides as Property Controlling Reagents in the Synthesis of Ceramic Materials
    journal, September 1994


    OLEX2 : a complete structure solution, refinement and analysis program
    journal, January 2009

    • Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
    • Journal of Applied Crystallography, Vol. 42, Issue 2
    • DOI: 10.1107/s0021889808042726

    ShelXle : a Qt graphical user interface for SHELXL
    journal, November 2011

    • Hübschle, Christian B.; Sheldrick, George M.; Dittrich, Birger
    • Journal of Applied Crystallography, Vol. 44, Issue 6
    • DOI: 10.1107/s0021889811043202

    A short history of SHELX
    journal, December 2007

    • Sheldrick, George M.
    • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
    • DOI: 10.1107/s0108767307043930

    Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
    journal, September 1976


    NMR and theoretical study on the linking properties of peroxovanadium(V) complexes with the 3-aminomethyl-pyridine derivatives
    journal, May 2017