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

Boyle, Timothy J.; Neville, Michael L.; Parkes, Marie V.

doi:10.1016/j.poly.2016.02.019

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

Journal Article · Thu Feb 11 00:00:00 EST 2016 · Polyhedron

DOI:https://doi.org/10.1016/j.poly.2016.02.019· OSTI ID:1239982

Boyle, Timothy J. ^[1]; Neville, Michael L. ^[2]; Parkes, Marie V. ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Univ. of California, San Diego, CA (United States)

In this study, a series of Group 4 phenoxy-thiols were developed from the reaction products of a series of metal tert-butoxides ([M(OBu^t)₄]) with four equivalents of 4-mercaptophenol (H-4MP). The products were found by single crystal X-ray diffraction to adopt the general structure [(HOBu^t)(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/OBu^t (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.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1239982

Alternate ID(s):: OSTI ID: 1341210

Report Number(s):: SAND-2015-11103J; PII: S0277538716001042

Journal Information:: Polyhedron, Vol. 110, Issue C; ISSN 0277-5387

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 3 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
alkoxides
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