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Title: Synthesis and structures of cadmium carboxylate and thiocarboxylate compounds with a sulfur-rich coordination environment: Carboxylate exchange kinetics involving tris(2-mercapto-1- t-butylimidazolyl)hydroborato cadmium complexes, [Tm But]Cd(O 2CR)

Abstract

Here, a series of cadmium carboxylate compounds in a sulfur-rich environment provided by the tris(2- tert-butylmercaptoimidazolyl)hydroborato ligand, namely, [Tm But]CdO 2CR, has been synthesized via the reactions of the cadmium methyl derivative [Tm But]CdMe with RCO 2H. Such compounds mimic aspects of cadmium-substituted zinc enzymes and also the surface atoms of cadmium chalcogenide crystals, and have therefore been employed to model relevant ligand exchange processes. Significantly, both 1H and 19F NMR spectroscopy demonstrate that the exchange of carboxylate groups between [Tm But]Cd(κ 2-O 2CR) and the carboxylic acid RCO 2H is facile on the NMR time scale, even at low temperature. Analysis of the rate of exchange as a function of concentration of RCO 2H indicates that reaction occurs via an associative rather than dissociative pathway. In addition to carboxylate compounds, the thiocarboxylate derivative [Tm But]Cd[κ 1-SC(O)Ph] has also been synthesized via the reaction of [Tm But]CdMe with thiobenzoic acid. The molecular structure of [Tm But]Cd[κ 1-SC(O)Ph] has been determined by X-ray diffraction, and an interesting feature is that, in contrast to the carboxylate derivatives [Tm But]Cd(κ 2-O 2CR), the thiocarboxylate ligand binds in a κ 1 manner via only the sulfur atom.

Authors:
 [1];  [1];  [1];  [1]
  1. Columbia Univ., New York, NY (United States)
Publication Date:
Research Org.:
Columbia Univ., New York, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1178615
Alternate Identifier(s):
OSTI ID: 1344911
Grant/Contract Number:  
SC0006410
Resource Type:
Published Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 8; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kreider-Mueller, Ava, Quinlivan, Patrick J., Owen, Jonathan S., and Parkin, Gerard. Synthesis and structures of cadmium carboxylate and thiocarboxylate compounds with a sulfur-rich coordination environment: Carboxylate exchange kinetics involving tris(2-mercapto-1- t-butylimidazolyl)hydroborato cadmium complexes, [TmBut]Cd(O2CR). United States: N. p., 2015. Web. doi:10.1021/acs.inorgchem.5b00017.
Kreider-Mueller, Ava, Quinlivan, Patrick J., Owen, Jonathan S., & Parkin, Gerard. Synthesis and structures of cadmium carboxylate and thiocarboxylate compounds with a sulfur-rich coordination environment: Carboxylate exchange kinetics involving tris(2-mercapto-1- t-butylimidazolyl)hydroborato cadmium complexes, [TmBut]Cd(O2CR). United States. doi:10.1021/acs.inorgchem.5b00017.
Kreider-Mueller, Ava, Quinlivan, Patrick J., Owen, Jonathan S., and Parkin, Gerard. Tue . "Synthesis and structures of cadmium carboxylate and thiocarboxylate compounds with a sulfur-rich coordination environment: Carboxylate exchange kinetics involving tris(2-mercapto-1- t-butylimidazolyl)hydroborato cadmium complexes, [TmBut]Cd(O2CR)". United States. doi:10.1021/acs.inorgchem.5b00017.
@article{osti_1178615,
title = {Synthesis and structures of cadmium carboxylate and thiocarboxylate compounds with a sulfur-rich coordination environment: Carboxylate exchange kinetics involving tris(2-mercapto-1- t-butylimidazolyl)hydroborato cadmium complexes, [TmBut]Cd(O2CR)},
author = {Kreider-Mueller, Ava and Quinlivan, Patrick J. and Owen, Jonathan S. and Parkin, Gerard},
abstractNote = {Here, a series of cadmium carboxylate compounds in a sulfur-rich environment provided by the tris(2-tert-butylmercaptoimidazolyl)hydroborato ligand, namely, [TmBut]CdO2CR, has been synthesized via the reactions of the cadmium methyl derivative [TmBut]CdMe with RCO2H. Such compounds mimic aspects of cadmium-substituted zinc enzymes and also the surface atoms of cadmium chalcogenide crystals, and have therefore been employed to model relevant ligand exchange processes. Significantly, both 1H and 19F NMR spectroscopy demonstrate that the exchange of carboxylate groups between [TmBut]Cd(κ2-O2CR) and the carboxylic acid RCO2H is facile on the NMR time scale, even at low temperature. Analysis of the rate of exchange as a function of concentration of RCO2H indicates that reaction occurs via an associative rather than dissociative pathway. In addition to carboxylate compounds, the thiocarboxylate derivative [TmBut]Cd[κ1-SC(O)Ph] has also been synthesized via the reaction of [TmBut]CdMe with thiobenzoic acid. The molecular structure of [TmBut]Cd[κ1-SC(O)Ph] has been determined by X-ray diffraction, and an interesting feature is that, in contrast to the carboxylate derivatives [TmBut]Cd(κ2-O2CR), the thiocarboxylate ligand binds in a κ1 manner via only the sulfur atom.},
doi = {10.1021/acs.inorgchem.5b00017},
journal = {Inorganic Chemistry},
number = 8,
volume = 54,
place = {United States},
year = {2015},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acs.inorgchem.5b00017

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Cited by: 3 works
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Works referencing / citing this record:

CCDC 1061406: Experimental Crystal Structure Determination: UHOLEK : (tris(3-t-butyl-2-thioxo-2,3-dihydro-1H-imidazol-1-yl)(hydrido)borate)-(4-phenylbutanoato)-cadmium
dataset, April 2015

  • Kreider-Mueller, Ava; Quinlivan, Patrick; Owen, Jonathan
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/cc14mgx4

CCDC 1061407: Experimental Crystal Structure Determination: UHOLIO : (tris(3-t-butyl-2-thioxo-2,3-dihydro-1H-imidazol-1-yl)(hydrido)borate)-(2,6-difluorobenzoato)-cadmium
dataset, April 2015

  • Kreider-Mueller, Ava; Quinlivan, Patrick J.; Owen, Jonathan S.
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/cc14mgy5