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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 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

    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