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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

Journal Article · · Inorganic Chemistry
 [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry, Columbia University, New York, New York 10027, United States
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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.

Research Organization:
Columbia Univ., New York, NY (United States)
Sponsoring Organization:
USDOE; National Institutes of Health (NIH)
Grant/Contract Number:
SC0006410; R01GM046502
OSTI ID:
1361437
Alternate ID(s):
OSTI ID: 1473847
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Vol. 56 Journal Issue: 8; ISSN 0020-1669
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Cited By (8)

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
New main-group ferrocenyldithiocarbamates and conversion to ferrocene oxazolidine-2-thione and -2-one journal January 2020
Heterogeneous Fenton-like activity of novel metallosalophen magnetic nanocomposites: significant anchoring group effect journal January 2019

Linked Research (6)

Figures / Tables (16)

Figure 1(p. 1)figure Figure 1
Figure 2(p. 2)figure Figure 2
Figure 3(p. 2)figure Figure 3
Scheme 1(p. 2)figure Scheme 1
Figure 4(p. 3)figure Figure 4
Figure 5(p. 3)figure Figure 5
Table 1(p. 3)table Table 1
Figure 6(p. 4)figure Figure 6
Figure 7(p. 4)figure Figure 7
Figure 8(p. 4)figure Figure 8
Scheme 2(p. 4)figure Scheme 2
Table 4(p. 4)table Table 4
Figure 9(p. 5)figure Figure 9
Figure 10(p. 6)figure Figure 10
Scheme 3(p. 6)figure Scheme 3
Table 5(p. 6)table Table 5

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY