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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},
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}
}

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