Synthesis, Structure and Conformational Properties of Fluoroformylchlorodifluoroacetyl Disulfide, FC(O)SSC(O)CF<sub>2</sub>Cl: Conformational Transferability in –C(O)SSC(O)– Compounds

Erben, Mauricio F.; Védova, Carlos O. Della; Willner, Helge; Boese, Roland

doi:10.1002/ejic.200600604

Cited by 14 publications

(10 citation statements)

References 41 publications

(58 reference statements)

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“…It is well-known that the ν(SS) stretching mode is usually observed in the Raman spectrum and can be used to characterize disulfide containing compounds. For CH 3 OC(O)SSCN the medium intensity signal appearing at 526 cm −1 is assigned to ν(SS), in agreement with reported values for other disulfide compounds. , …”

Section: Ch3oc(o)sscnsupporting

confidence: 90%

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Conformational Behavior of CH₃OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study

Torrico-Vallejos

Erben

et al. 2010

J. Phys. Chem. A

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Pure methoxycarbonylsulfenyl cyanide, CH(3)OC(O)SCN (I), and methoxycarbonylsulfenyl thiocyanate, CH(3)OC(O)SSCN (II), were prepared by reacting liquid CH(3)OC(O)SCl with either AgCN or AgSCN, respectively. Compounds I and II were characterized by (1)H NMR, CG-MS, and vibrational (FTIR and FT-Raman) techniques. The conformational properties have been studied by using vibrational spectroscopy [infrared (gaseous, liquid, and Ar matrix isolated), Raman (liquid) spectroscopy] together with quantum chemical calculations at the B3LYP and MP2 methods with the extended 6-311++G** and aug-cc-pVTZ basis sets. Compound I exhibits a conformational equilibrium at room temperature having the most stable form C(s) symmetry with a synperiplanar (syn) orientation of the carbonyl double bond (C=O) with respect to both the CH(3)O- and -SCN groups (syn-syn). Several bands assigned to a second conformer have been observed in the IR matrix spectra. This rotamer presents an antiperiplanar orientation of the thiocyanate group (syn-anti). Evaluating the equilibrium compositions at different temperatures by quenching the gas phase mixtures as Ar matrices allowed us to determine the conformational enthalpy difference DeltaH(0) = H(0)((syn-anti)) - H(0)((syn-syn)) = 0.80(18) kcal mol(-1). A similar conformational behavior has been determined for compound II. Thermodynamic properties were also computed at the high-level G2MP2 and G3 model chemistry methods. The importance of mesomeric (resonance) and anomeric (hyperconjugation) electronic interaction in the conformational behavior is evaluated by using the NBO approach for both species.

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Section: Ch3oc(o)sscnsupporting

confidence: 90%

“…For CH 3 OC(O)SSCN the medium intensity signal appearing at 526 cm -1 is assigned to ν(SsS), in agreement with reported values for other disulfide compounds. 34,54…”

Section: Ch 3 Oc(o)sscnmentioning

confidence: 99%

Conformational Behavior of CH₃OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study

Torrico-Vallejos

Erben

et al. 2010

J. Phys. Chem. A

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“…The formation of chlorodifluoroacetyl disulfides of the type CF 2 ClC(O)SSR also becomes feasible by the reaction of CF 2 ClC(O)SH with sulfenyl chlorides 9. Thus, the title compound reacts quantitatively by Haas' chemistry with FC(O)SCl, ClC(O)SCl and CCl 3 SCl to yield several new disulfides, CF 2 ClC(O)SSC(O)F,21 CF 2 ClC(O)SSC(O)Cl and CF 2 ClC(O)SSCCl 3 , respectively 20,22…”

Section: Resultsmentioning

confidence: 99%

Chlorodifluorothioacetic Acid, CF₂ClC(O)SH: Synthesis, Characterization, X‐ray Structure and Conformational Properties

et al. 2007

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Chlorodifluoroacetic anhydride, [CF2ClC(O)]2O, and chlorodifluoroacetyl chloride, CF2ClC(O)Cl, react with hydrogen sulfide to yield chlorodifluorothioacetic acid, CF2ClC(O)SH. This novel thiocarboxylic acid has been obtained in pure form and characterized by NMR, IR and Raman spectroscopy. By extrapolation of the vapour pressure curve, log p = 6.102–2068/T (p [bar], T [K]), the boiling point was determined to be 66(1) °C. The melting point of the pure substance is –83(2) °C. The conformational properties of the gas‐phase molecule have been studied by vibrational spectroscopy [IR (vapour), Raman (liquid)] and quantum chemical calculations [B3LYP and MP2 methods with 6‐311++G(d,p) and 6‐311++G(3df,2p) basis sets]. The most stable form has C1 symmetry with a synperiplanar (syn) orientation of the C=O double bond with respect to the S–H single bond whereas in the chlorodifluoroacetyl group the gauche orientation of the ClC–C=O moiety is preferred (gauche‐syn form). The analysis of the IR spectrum of gaseous CF2ClC(O)SH suggests the presence of two other conformations in equilibrium at room temperature. These forms have been fully characterized by high‐level quantum chemical calculations. The structure of a single crystal, grown by a miniature zone‐melting procedure using focused infrared laser radiation, was determined by X‐ray diffraction analysis at low temperature. The crystalline solid [monoclinic, space group C2/c, a = 17.6165(14), b = 5.8848(5), c = 11.0877(9) Å, β = 113.5330(11)°] consists exclusively of molecules adopting the gauche‐syn conformation. These molecules associate, forming pairs of cyclic dimers in the crystal through S–H···O=C hydrogen bonds.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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“…Previous studies reported for disulfide containing compounds of the type RSSR reveal that dihedral angles smaller than 901 are observed in disulfides attached to two carbon atoms with sp 2 hybridization; if both carbon substituents are sp 3 -hybridized, the dihedral angle is larger than 1201. [30][31][32] An intermediate angle has been observed in CH 3 OC(O)SSCF 3 , which contains both sp 3 -and sp 2 -hybridized carbon atoms bonded to the disulfide bond.…”

Section: Discussionmentioning

confidence: 99%

“…38 We have identified such short 1,4 SÁ Á ÁO contacts in a series of acyl disulfides, where intramolecular interactions between the CQO and S-S groups may be present. 31,32 For the title compound a 1,4 SÁ Á ÁO intramolecular average distance of 3.116 A ˚defined by the sulfur atom attached to the CF 3 group and the oxygen atom of the carbonyl group is observed (see Fig. 8).…”

Section: Crystal Structurementioning

confidence: 95%

Methoxycarbonyl trifluoromethyl disulfide, CH3OC(O)SSCF3: synthesis, structure and conformational properties

et al. 2010

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Synthesis, Structure and Conformational Properties of Fluoroformylchlorodifluoroacetyl Disulfide, FC(O)SSC(O)CF₂Cl: Conformational Transferability in –C(O)SSC(O)– Compounds

Cited by 14 publications

References 41 publications

Conformational Behavior of CH₃OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study

Conformational Behavior of CH₃OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study

Chlorodifluorothioacetic Acid, CF₂ClC(O)SH: Synthesis, Characterization, X‐ray Structure and Conformational Properties

Methoxycarbonyl trifluoromethyl disulfide, CH3OC(O)SSCF3: synthesis, structure and conformational properties

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Synthesis, Structure and Conformational Properties of Fluoroformylchlorodifluoroacetyl Disulfide, FC(O)SSC(O)CF2Cl: Conformational Transferability in –C(O)SSC(O)– Compounds

Cited by 14 publications

References 41 publications

Conformational Behavior of CH3OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study

Conformational Behavior of CH3OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study

Chlorodifluorothioacetic Acid, CF2ClC(O)SH: Synthesis, Characterization, X‐ray Structure and Conformational Properties

Methoxycarbonyl trifluoromethyl disulfide, CH3OC(O)SSCF3: synthesis, structure and conformational properties

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Synthesis, Structure and Conformational Properties of Fluoroformylchlorodifluoroacetyl Disulfide, FC(O)SSC(O)CF₂Cl: Conformational Transferability in –C(O)SSC(O)– Compounds

Conformational Behavior of CH₃OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study

Conformational Behavior of CH₃OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study

Chlorodifluorothioacetic Acid, CF₂ClC(O)SH: Synthesis, Characterization, X‐ray Structure and Conformational Properties