Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [Tm Bu t ]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment

Kreider-Mueller, Ava; Quinlivan, Patrick J.; Owen, Jonathan S.; Parkin, Gerard

doi:10.1021/acs.inorgchem.7b00296

Title: Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [Tm ^{Bu ^t} ]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment

Abstract

A series of cadmium thiolate compounds that feature a sulfur-rich coordination environment, namely [Tm^{Bu^t}]CdSAr, have been synthesized by the reactions of [Tm^{Bu^t}]CdMe with ArSH (Ar = C₆H₄-4-F, C₆H₄-4-Bu^t, C₆H₄-4-OMe, and C₆H₄-3-OMe). In addition, the pyridine-2-thiolate and pyridine-2-selenolate derivatives, [Tm ^{Bu^t}]CdSPy and [Tm^{Bu^t}]CdSePy have been obtained via the respective reactions of [Tm^{Bu^t}]CdMe with pyridine-2-thione and pyridine-2-selone. The molecular structures of [Tm^{Bu^t}]CdSAr and [Tm^{Bu^t}]CdEPy (E = S or Se) have been determined by X-ray diffraction and demonstrate that, in each case, the [CdS₄] motif is distorted tetrahedral and approaches a trigonal monopyramidal geometry in which the thiolate ligand adopts an equatorial position; [Tm^{Bu^t}]CdSPy and [Tm^{Bu^t}]CdSePy, however, exhibit an additional long-range interaction with the pyridyl nitrogen atoms. The ability of the thiolate ligands to participate in exchange was probed by ¹H and ¹⁹F nuclear magnetic resonance (NMR) spectroscopic studies of the reactions of [Tm^{Bu^t}]CdSC₆H₄-4-F with ArSH (Ar = C₆H₄-4-Bu^t or C₆H₄-4-OMe), which demonstrate that (i) exchange is facile and (ii) coordination of thiolate to cadmium is most favored for the p-fluorophenyl derivative. Furthermore, a two-dimensional EXSY experiment involving [Tm^{Bu^t}]CdSC₆H₄-4-F and 4-fluorothiophenol demonstrates that degenerate thiolate ligand exchange is also facile on the NMR time scale.

Authors:

Kreider-Mueller, Ava ^[1]; Quinlivan, Patrick J. ^[1];

^[1];

^[1]

Department of Chemistry, Columbia University, New York, New York 10027, United States

Publication Date:: Mon Apr 03 00:00:00 EDT 2017

Research Org.:: Columbia Univ., New York, NY (United States)

Sponsoring Org.:: USDOE; National Institutes of Health (NIH)

OSTI Identifier:: 1361437

Alternate Identifier(s):: OSTI ID: 1473847

Grant/Contract Number:: SC0006410; R01GM046502

Resource Type:: Published Article

Journal Name:: Inorganic Chemistry

Additional Journal Information:: Journal Name: Inorganic Chemistry Journal Volume: 56 Journal Issue: 8; Journal ID: ISSN 0020-1669

Publisher:: American Chemical Society

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. Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [Tm Bu t ]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment.  United States: N. p., 2017. 
Web.  doi:10.1021/acs.inorgchem.7b00296.

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                    Kreider-Mueller, Ava, Quinlivan, Patrick J., Owen, Jonathan S., & Parkin, Gerard. Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [Tm Bu t ]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment.  United States.  https://doi.org/10.1021/acs.inorgchem.7b00296

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                    Kreider-Mueller, Ava, Quinlivan, Patrick J., Owen, Jonathan S., and Parkin, Gerard. Mon .  
"Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [Tm Bu t ]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment".  United States.  https://doi.org/10.1021/acs.inorgchem.7b00296.

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@article{osti_1361437,

  title        = {Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [Tm Bu t ]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment},

  author       = {Kreider-Mueller, Ava and Quinlivan, Patrick J. and Owen, Jonathan S. and Parkin, Gerard},

  abstractNote = {A series of cadmium thiolate compounds that feature a sulfur-rich coordination environment, namely [TmBut]CdSAr, have been synthesized by the reactions of [TmBut]CdMe with ArSH (Ar = C6H4-4-F, C6H4-4-But, C6H4-4-OMe, and C6H4-3-OMe). In addition, the pyridine-2-thiolate and pyridine-2-selenolate derivatives, [Tm But]CdSPy and [TmBut]CdSePy have been obtained via the respective reactions of [TmBut]CdMe with pyridine-2-thione and pyridine-2-selone. The molecular structures of [TmBut]CdSAr and [TmBut]CdEPy (E = S or Se) have been determined by X-ray diffraction and demonstrate that, in each case, the [CdS4] motif is distorted tetrahedral and approaches a trigonal monopyramidal geometry in which the thiolate ligand adopts an equatorial position; [TmBut]CdSPy and [TmBut]CdSePy, however, exhibit an additional long-range interaction with the pyridyl nitrogen atoms. The ability of the thiolate ligands to participate in exchange was probed by 1H and 19F nuclear magnetic resonance (NMR) spectroscopic studies of the reactions of [TmBut]CdSC6H4-4-F with ArSH (Ar = C6H4-4-But or C6H4-4-OMe), which demonstrate that (i) exchange is facile and (ii) coordination of thiolate to cadmium is most favored for the p-fluorophenyl derivative. Furthermore, a two-dimensional EXSY experiment involving [TmBut]CdSC6H4-4-F and 4-fluorothiophenol demonstrates that degenerate thiolate ligand exchange is also facile on the NMR time scale.},

  doi          = {10.1021/acs.inorgchem.7b00296},

  journal      = {Inorganic Chemistry},

  number       = 8,

  volume       = 56,

  place        = {United States},

  year         = {Mon Apr 03 00:00:00 EDT 2017},

  month        = {Mon Apr 03 00:00:00 EDT 2017}

}

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Cited by: 7 works

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Figure 1: [Tm^R] ligands in their κ³ coordination mode.

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Works referencing / citing this record:

CCDC 1549719: Experimental Crystal Structure Determination: HAQDOV : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(3-methoxybenzene-1-thiolato)-cadmium(ii) benzene solvate
dataset, May 2017

Kreider-Mueller, Ava; Quinlivan, Patrick J.; Owen, Jonathan S.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1p0ly7

CCDC 1549720: Experimental Crystal Structure Determination: HAQDUB : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(4-methoxybenzene-1-thiolato)-cadmium(ii) benzene solvate
dataset, May 2017

Kreider-Mueller, Ava; Quinlivan, Patrick J.; Owen, Jonathan S.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1p0lz8

CCDC 1549721: Experimental Crystal Structure Determination: HAQFAJ : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(4-t-butylbenzenehthiolato)-cadmium(ii)
dataset, May 2017

Kreider-Mueller, Ava; Quinlivan, Patrick J.; Owen, Jonathan S.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1p0m0b

CCDC 1549722: Experimental Crystal Structure Determination: HAQFEN : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(pyridine-2-selenolato)-cadmium(ii)
dataset, May 2017

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Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1p0m1c

CCDC 1549723: Experimental Crystal Structure Determination: HAQFIR : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(4-fluorobenzene-1-thiolato)-cadmium(ii)
dataset, May 2017

Kreider-Mueller, Ava; Quinlivan, Patrick J.; Owen, Jonathan S.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1p0m2d

CCDC 1549724: Experimental Crystal Structure Determination: HAQFOX : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(pyridine-2-thiolato)-cadmium(ii)
dataset, May 2017

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DOI: 10.5517/ccdc.csd.cc1p0m3f

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Title: Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [Tm Bu t ]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment

Abstract

Citation Formats

Figures / Tables:

CCDC 1549719: Experimental Crystal Structure Determination: HAQDOV : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(3-methoxybenzene-1-thiolato)-cadmium(ii) benzene solvate dataset, May 2017

CCDC 1549720: Experimental Crystal Structure Determination: HAQDUB : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(4-methoxybenzene-1-thiolato)-cadmium(ii) benzene solvate dataset, May 2017

CCDC 1549721: Experimental Crystal Structure Determination: HAQFAJ : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(4-t-butylbenzenehthiolato)-cadmium(ii) dataset, May 2017

CCDC 1549722: Experimental Crystal Structure Determination: HAQFEN : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(pyridine-2-selenolato)-cadmium(ii) dataset, May 2017

CCDC 1549723: Experimental Crystal Structure Determination: HAQFIR : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(4-fluorobenzene-1-thiolato)-cadmium(ii) dataset, May 2017

CCDC 1549724: Experimental Crystal Structure Determination: HAQFOX : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(pyridine-2-thiolato)-cadmium(ii) dataset, May 2017

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Title: Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [Tm ^{Bu ^t} ]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment

CCDC 1549719: Experimental Crystal Structure Determination: HAQDOV : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(3-methoxybenzene-1-thiolato)-cadmium(ii) benzene solvate
dataset, May 2017

CCDC 1549720: Experimental Crystal Structure Determination: HAQDUB : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(4-methoxybenzene-1-thiolato)-cadmium(ii) benzene solvate
dataset, May 2017

CCDC 1549721: Experimental Crystal Structure Determination: HAQFAJ : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(4-t-butylbenzenehthiolato)-cadmium(ii)
dataset, May 2017

CCDC 1549722: Experimental Crystal Structure Determination: HAQFEN : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(pyridine-2-selenolato)-cadmium(ii)
dataset, May 2017

CCDC 1549723: Experimental Crystal Structure Determination: HAQFIR : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(4-fluorobenzene-1-thiolato)-cadmium(ii)
dataset, May 2017

CCDC 1549724: Experimental Crystal Structure Determination: HAQFOX : (3,3',3''-(hydrogen boratetriyl)tris(1-t-butyl-1H-3-imidazole-2-thiolato))-(pyridine-2-thiolato)-cadmium(ii)
dataset, May 2017

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