Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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-(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.

Authors:
 [1];  [1]
+ Show Author Affiliations
  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:
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.
Copy to clipboard
Boyle, Timothy J., & Sivonxay, Eric. Synthesis and characterization of 2-hydroxy-pyridine modified Group 4 alkoxides. United States. https://doi.org/10.1080/00958972.2016.1183253
Copy to clipboard
Boyle, Timothy J., and Sivonxay, Eric. Thu . "Synthesis and characterization of 2-hydroxy-pyridine modified Group 4 alkoxides". United States. https://doi.org/10.1080/00958972.2016.1183253. https://www.osti.gov/servlets/purl/1339287.
Copy to clipboard
@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},
number = 9,
volume = 69,
place = {United States},
year = {Thu May 19 00:00:00 EDT 2016},
month = {Thu May 19 00:00:00 EDT 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1080/00958972.2016.1183253
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

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

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

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

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

Chemical Vapor Deposition
journal, January 2016

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 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 3 (μ 3 -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

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

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

Heterometallic Alkoxides
book, January 2001

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

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

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

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(IV) Neopentoxides. X-ray Structures of Ti 3 (μ 3 -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

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

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

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

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

Advanced Materials Research Vols. 11-12
journal, February 2006

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

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

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

Chemical Vapor Deposition
book, January 2002

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    NMR study on the coordination of diperoxovanadium(V) complexes with 2-hydroxymethyl pyridine derivatives
    journal, September 2018

    Synthesis, characterization, and computational modeling of 6,6'-(((2-hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) modified group 4 metal alkoxides
    journal, May 2020

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

      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections:

      Other research related to this record: