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Title: Synthesis and characterization of a series of Group 4 phenoxy-thiol derivatives

Abstract

In this study, a series of Group 4 phenoxy-thiols were developed from the reaction products of a series of metal tert-butoxides ([M(OBut)4]) with four equivalents of 4-mercaptophenol (H-4MP). The products were found by single crystal X-ray diffraction to adopt the general structure [(HOBut)(4MP)3M(μ-4MP)]2 [where M = Ti (1), Zr (2), Hf (3)] from toluene and [(py)2M(4MP)] where M = Ti (4), Zr (5) and [(py)(4MP)3Hf(μ-4MP)]2 (6) from pyridine (py). Varying the [Ti(OR)4] precursors (OR = iso-propoxide (OPri) or neo-pentoxide (ONep)) in toluene led to [(HOR)(4MP)3Ti(μ-4MP)]2 (OR = OPri (7), ONep (8)), which were structurally similar to 1. Lower stoichiometric reactions in toluene led to partial substitution by the 4MP ligands yielding [H][Ti(μ-4MP)(4MP)(ONep)3]2 (9). Independent of the stoichiometry, all of the Ti derivatives were found to be red in color, whereas the heavier congeners were colorless. Attempts to understand this phenomenon led to investigation with a series of varied –SH substituted phenols. From the reaction of H-2MP and H-3MP (2-mercaptophenol and 3-mercaptophenol, respectively), the isolated products had identical arrangements: [(ONep)2(2MP)Ti(μ,η2-2MP)]2 (10) and [(HOR)(3MP)M(μ-3MP)]2 (M/OR = Ti/ONep (11); Zr/OBut (12)) with a similar red color. Based on the simulated and observed UV–Vis spectra, it was reasoned that the color was generated duemore » to a ligand-to-metal charge transfer for Ti that was not available for the larger congeners.« less

Authors:
 [1];  [2];  [1]
+ Show Author Affiliations
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Univ. of California, San Diego, CA (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:
1239982
Alternate Identifier(s):
OSTI ID: 1341210
Report Number(s):
SAND-2015-11103J
Journal ID: ISSN 0277-5387; PII: S0277538716001042
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Polyhedron
Additional Journal Information:
Journal Volume: 110; Journal Issue: C; Journal ID: ISSN 0277-5387
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alkoxides; thiols; titanium; zirconium; hafnium

Citation Formats

Boyle, Timothy J., Neville, Michael L., and Parkes, Marie V. Synthesis and characterization of a series of Group 4 phenoxy-thiol derivatives. United States: N. p., 2016. Web. doi:10.1016/j.poly.2016.02.019.
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Boyle, Timothy J., Neville, Michael L., & Parkes, Marie V. Synthesis and characterization of a series of Group 4 phenoxy-thiol derivatives. United States. https://doi.org/10.1016/j.poly.2016.02.019
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Boyle, Timothy J., Neville, Michael L., and Parkes, Marie V. Thu . "Synthesis and characterization of a series of Group 4 phenoxy-thiol derivatives". United States. https://doi.org/10.1016/j.poly.2016.02.019. https://www.osti.gov/servlets/purl/1239982.
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@article{osti_1239982,
title = {Synthesis and characterization of a series of Group 4 phenoxy-thiol derivatives},
author = {Boyle, Timothy J. and Neville, Michael L. and Parkes, Marie V.},
abstractNote = {In this study, a series of Group 4 phenoxy-thiols were developed from the reaction products of a series of metal tert-butoxides ([M(OBut)4]) with four equivalents of 4-mercaptophenol (H-4MP). The products were found by single crystal X-ray diffraction to adopt the general structure [(HOBut)(4MP)3M(μ-4MP)]2 [where M = Ti (1), Zr (2), Hf (3)] from toluene and [(py)2M(4MP)] where M = Ti (4), Zr (5) and [(py)(4MP)3Hf(μ-4MP)]2 (6) from pyridine (py). Varying the [Ti(OR)4] precursors (OR = iso-propoxide (OPri) or neo-pentoxide (ONep)) in toluene led to [(HOR)(4MP)3Ti(μ-4MP)]2 (OR = OPri (7), ONep (8)), which were structurally similar to 1. Lower stoichiometric reactions in toluene led to partial substitution by the 4MP ligands yielding [H][Ti(μ-4MP)(4MP)(ONep)3]2 (9). Independent of the stoichiometry, all of the Ti derivatives were found to be red in color, whereas the heavier congeners were colorless. Attempts to understand this phenomenon led to investigation with a series of varied –SH substituted phenols. From the reaction of H-2MP and H-3MP (2-mercaptophenol and 3-mercaptophenol, respectively), the isolated products had identical arrangements: [(ONep)2(2MP)Ti(μ,η2-2MP)]2 (10) and [(HOR)(3MP)M(μ-3MP)]2 (M/OR = Ti/ONep (11); Zr/OBut (12)) with a similar red color. Based on the simulated and observed UV–Vis spectra, it was reasoned that the color was generated due to a ligand-to-metal charge transfer for Ti that was not available for the larger congeners.},
doi = {10.1016/j.poly.2016.02.019},
journal = {Polyhedron},
number = C,
volume = 110,
place = {United States},
year = {Thu Feb 11 00:00:00 EST 2016},
month = {Thu Feb 11 00:00:00 EST 2016}
}
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