Vibrational frequencies and structural determination of thiocyanogen

Jensen, James O.

doi:10.1016/j.theochem.2004.09.046

Cited by 8 publications

(11 citation statements)

References 27 publications

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“…Instead, it resulted in the appearance of a new sharp ν(CN) band at 2063 cm –1 (Figure , black line). This could be due to formation of free [NCS]¯ (the S–S bond is known to be weak), decomposition to form [CN]¯, or formation of the relatively long-lived [NCS] 2 •– . The UV–vis spectrum (Figure ) shows no evidence of [NCS] 2 •– that features a characteristic absorbance at 480 nm .…”

Section: Resultsmentioning

confidence: 99%

“…[NCS]¯ (the S-S bond is known to be weak 54 an OTTLE cell. Spectra: Red -parent [1] 3-, green -after the irreversible oxidation to producing (among others) (NCS)2 (λmax = 320 nm); black -after the back reduction of (NCS)2 producing mainly [Et4N]3 [3]).…”

Section: Electrochemical and Spectroelectrochemical Studiesmentioning

confidence: 99%

“…Instead, it resulted in the appearance of a new sharp ν(CN) band at 2063 cm −1 (Figure 10, black line). This could be due to formation of free [NCS]¯(the S−S bond is known to be weak 54 ), decomposition to form [CN]¯, 55 that features a characteristic absorbance at 480 nm. 28 The disappearance of the f−f transitions reflects a decomposition of the parent U(IV) complex.…”

Section: Attempts To Obtain a Photoluminescence Spectrum Of [Et 4 N] ...mentioning

confidence: 99%

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Thiocyanate Complexes of Uranium in Multiple Oxidation States: A Combined Structural, Magnetic, Spectroscopic, Spectroelectrochemical, and Theoretical Study

et al. 2014

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A comprehensive study of the complexes A4[U(NCS)8] (A = Cs, Et4N, (n)Bu4N) and A3[UO2(NCS)5] (A = Cs, Et4N) is described, with the crystal structures of [(n)Bu4N]4[U(NCS)8]·2MeCN and Cs3[UO2(NCS)5]·O0.5 reported. The magnetic properties of square antiprismatic Cs4[U(NCS)8] and cubic [Et4N]4[U(NCS)8] have been probed by SQUID magnetometry. The geometry has an important impact on the low-temperature magnetic moments: at 2 K, μeff = 1.21 μB and 0.53 μB, respectively. Electronic absorption and photoluminescence spectra of the uranium(IV) compounds have been measured. The redox chemistry of [Et4N]4[U(NCS)8] has been explored using IR and UV-vis spectroelectrochemical methods. Reversible 1-electron oxidation of one of the coordinated thiocyanate ligands occurs at +0.22 V vs Fc/Fc(+), followed by an irreversible oxidation to form dithiocyanogen (NCS)2 which upon back reduction regenerates thiocyanate anions coordinating to UO2(2+). NBO calculations agree with the experimental spectra, suggesting that the initial electron loss of [U(NCS)8](4-) is delocalized over all NCS(-) ligands. Reduction of the uranyl(VI) complex [Et4N]3[UO2(NCS)5] to uranyl(V) is accompanied by immediate disproportionation and has only been studied by DFT methods. The bonding in [An(NCS)8](4-) (An = Th, U) and [UO2(NCS)5](3-) has been explored by a combination of DFT and QTAIM analysis, and the U-N bonds are predominantly ionic, with the uranyl(V) species more ionic that the uranyl(VI) ion. Additionally, the U(IV)-NCS ion is more ionic than what was found for U(IV)-Cl complexes.

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Section: Resultsmentioning

confidence: 99%

Section: Electrochemical and Spectroelectrochemical Studiesmentioning

confidence: 99%

Section: Attempts To Obtain a Photoluminescence Spectrum Of [Et 4 N] ...mentioning

confidence: 99%

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Thiocyanate Complexes of Uranium in Multiple Oxidation States: A Combined Structural, Magnetic, Spectroscopic, Spectroelectrochemical, and Theoretical Study

et al. 2014

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“…The typical absorption of disulfide bonds at 525 cm −1 was disappeared in cured resins. 56 The new absorption band at 683 cm −1 was attributed to the formation of C−S bonds. 56 These results indicated that disulfide bonds were involved in the polymerization of the system.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Self-Curing Phthalonitrile Resin with Disulfide Bond as the Curing Group

Hu,

Pu,

Zhou

et al. 2023

ACS Appl. Polym. Mater.

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To further investigate the presence of a radical mechanism in the curing process of phthalonitrile resins, a conventional radical initiation unit (disulfide segment) was introduced into phthalonitrile resins for the first time. A disulfide-bond-containing phthalonitrile monomer (DPBPN) was successfully synthesized. Its self-curing reaction could be promoted by disulfide segments in the precursor. Rheological measurements and differential scanning calorimetry showed that DPBPN exhibited a low melting point (124.5 °C) and a wide processing window (120 °C). Infrared spectroscopy confirmed the formation of isoindoline, triazine, and phthalocyanine structures in the product. Thermal gravimetric analysis and dynamic mechanical analysis suggested the outstanding thermal stability and high glass transition temperature (T g) of the cured resin with a moderate curing process.

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“…The geometries of B 12 H 12 2− , 1 , and 2 were taken from the relevant crystal structures (CSD code FUYZOO for B 12 H 12 2− , ZASYEX for 1 , or this work for 2b ), while 2a and 2c geometries were built by analogy. The structure of (SCN) 2 was built according to ref .…”

Section: Methodsmentioning

confidence: 99%

Thiocyanation of closo-Dodecaborate B₁₂H₁₂²⁻. A Novel Synthetic Route and Theoretical Elucidation of the Reaction Mechanism

et al. 2010

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Although vast experimental experience has been accumulated about the reactions of icosahedral B(12)H(12)(2-) borane cages, little is known about the mechanisms by which these reactions proceed. To address this issue, we have chosen the thiocyanation of B(12)H(12)(2-) and have studied this reaction using both experimental and theoretical methods. First, we present a novel and more convenient synthetic route using in situ generated thiocyanogen, (SCN)(2). The synthesized disubstituted product B(12)H(10)(SCN)(2)(2-) is exclusively the meta positional isomer, as confirmed by the X-ray crystallographic analysis. The quantum chemical calculations at the B3LYP/def2-TZVP//RI-PBE/def2-SVP level show that the free energy differences between the ortho, meta, and para disubstituted species are very small and as such cannot explain the observed positional preferences. The calculations of the kinetic aspects reveal that the reaction is best described as an electrophilic substitution. The calculated isomer preferences for the second SCN substituent are meta > para > ortho. The major outcome of this work is a clear and consistent picture of the electrophilic substitution reaction mechanism of the thiocyanation of B(12)H(12)(2-), thus contributing to our understanding of the general features of boron hydride reactivity.

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Vibrational frequencies and structural determination of thiocyanogen

Cited by 8 publications

References 27 publications

Thiocyanate Complexes of Uranium in Multiple Oxidation States: A Combined Structural, Magnetic, Spectroscopic, Spectroelectrochemical, and Theoretical Study

Thiocyanate Complexes of Uranium in Multiple Oxidation States: A Combined Structural, Magnetic, Spectroscopic, Spectroelectrochemical, and Theoretical Study

Self-Curing Phthalonitrile Resin with Disulfide Bond as the Curing Group

Thiocyanation of closo-Dodecaborate B₁₂H₁₂²⁻. A Novel Synthetic Route and Theoretical Elucidation of the Reaction Mechanism

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Vibrational frequencies and structural determination of thiocyanogen

Cited by 8 publications

References 27 publications

Thiocyanate Complexes of Uranium in Multiple Oxidation States: A Combined Structural, Magnetic, Spectroscopic, Spectroelectrochemical, and Theoretical Study

Thiocyanate Complexes of Uranium in Multiple Oxidation States: A Combined Structural, Magnetic, Spectroscopic, Spectroelectrochemical, and Theoretical Study

Self-Curing Phthalonitrile Resin with Disulfide Bond as the Curing Group

Thiocyanation of closo-Dodecaborate B12H122−. A Novel Synthetic Route and Theoretical Elucidation of the Reaction Mechanism

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Thiocyanation of closo-Dodecaborate B₁₂H₁₂²⁻. A Novel Synthetic Route and Theoretical Elucidation of the Reaction Mechanism