2006
DOI: 10.1021/ic060719t
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Dioxotungsten 1,2-Benzenedithiolate Complex Stabilized by NH···S Hydrogen Bonds

Abstract: Novel dioxo-tungsten(VI) bis(1,2-benzenedithiolate) complexes with neighboring amide groups, as models for tungsten enzymes, (NEt4)2[W(VI)O2{1,2-S(2)-3,6-(RCONH)2C6H2}2] (R = CH3, t-Bu), were designed and synthesized. The presence of the NH...S hydrogen bond was confirmed through IR spectrometry and X-ray crystallographic analysis. In the W(VI)O2 complexes, the NH...S hydrogen bond trans to the oxo ligand is stronger than that cis to oxo. On the basis of comparisons with [W(VI)O2(1,2-S2C6H4)2](2-), the NH...S … Show more

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Cited by 28 publications
(115 citation statements)
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“…The two intramolecular hydrogen bond might suggest a proton transfer pathway from amine of phosphine ligand to the sulfur atom of active site. Although the SÁÁÁH distance for the intramolecular is longer than that of typically sulfur hydrogen bond [30,31], it may influence the skeleton of 2Fe2S whose distance (3.049 Å) of non-bonded two sulfur atoms for 6 is slightly longer than that of two sulfur atoms for 5 (3.03 Å) and for 7 (3.042 Å).…”
Section: Molecular Structures Of Complexes 5-7mentioning
confidence: 98%
“…The two intramolecular hydrogen bond might suggest a proton transfer pathway from amine of phosphine ligand to the sulfur atom of active site. Although the SÁÁÁH distance for the intramolecular is longer than that of typically sulfur hydrogen bond [30,31], it may influence the skeleton of 2Fe2S whose distance (3.049 Å) of non-bonded two sulfur atoms for 6 is slightly longer than that of two sulfur atoms for 5 (3.03 Å) and for 7 (3.042 Å).…”
Section: Molecular Structures Of Complexes 5-7mentioning
confidence: 98%
“…For example, a Co(II)-thiolate complex has a tetrahedral geometry with a strong intramolecular NHÁ Á ÁS hydrogen bond (Figure 27.8(c)). [53,54]. In the W VI O 2 complexes, the NHÁ Á ÁS hydrogen bond trans to the oxo ligand is stronger than that cis to the ligand.…”
Section: Regulation Of Thiolate and Phenolate Ligands In Metal Complementioning
confidence: 96%
“…The CpWO 2 X structure has been previously reported for crystallographically characterized compounds only with O-based or C-based X ligands. [29]. In the two latter compounds, the trans S donors (trans to an oxo ligand) show even longer WeS bonds, 2.581(2), 2.586(2) [28] and 2.607(3) Å [29].…”
Section: Mercaptopropionic Acidmentioning
confidence: 99%
“…[29]. In the two latter compounds, the trans S donors (trans to an oxo ligand) show even longer WeS bonds, 2.581(2), 2.586(2) [28] and 2.607(3) Å [29]. In all the other above-cited molecules, the SR donors are mutually trans.…”
Section: Mercaptopropionic Acidmentioning
confidence: 99%