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Conformational Behavior of CH3OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study
Torrico-Vallejos, Sonia1; Erben, Mauricio F.1; Ge, Mao-Fa2; Willner, Helge3; Della Vedova, Carlos O.1,4
2010-03-18
Source PublicationJOURNAL OF PHYSICAL CHEMISTRY A
ISSN1089-5639
Volume114Issue:10Pages:3703-3712
AbstractPure methoxycarbonylsulfenyl cyanide, CH3OC(O)SCN (I), and rnethoxycarbortylsulfenyl thiocyanate, CH3OC(O)SSCN (II), were prepared by reacting liquid CH3OC(O)SCl with either AgCN or AgSCN, respectively. Compounds I and II were characterized by H-1 NMR, CG-MS, and vibrational (FTIR and FT-Raman) techniques. The conformational properties have been Studied by using vibrational spectroscopy I 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 1 exhibits a conformational equilibrium at room temperature having the most stable form C, symmetry with a synperiplanar (syn) orientation of the carbonyl double bond (C=O) with respect to both the CH3O- and -SCN groups (syn-syn). Several bands assigned to a second conformer have been observed ill 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 LIS to determine the conformational enthalpy difference Delta H-0 = H-(syn-anti)(0) - H-(syn-syn)(0) = 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.
DOI10.1021/jp912044r
Indexed BySCI
Language英语
WOS IDWOS:000275327600041
PublisherAMER CHEMICAL SOC
Citation statistics
Cited Times:10[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/71212
Collection中国科学院化学研究所
Corresponding AuthorErben, Mauricio F.
Affiliation1.Univ Nacl La Plata, Fac Ciencias Exactas, Dept Quim, CONICET,UNLP,CEQUINOR, Buenos Aires, DF, Argentina
2.Chinese Acad Sci, Inst Chem, State Key Lab Struct Chem Unstable & Stable Speci, Beijing 100080, Peoples R China
3.Berg Univ Gesamthsch Wuppertal, Fachbereich C Anorgan Chem, D-47097 Wuppertal, Germany
4.Consejo Nacl Invest Cient & Tecn, CIC, UNLP, Lab Serv Ind & Sistema Cient LaSeISiC, RA-1903 Gonnet, Argentina
Recommended Citation
GB/T 7714
Torrico-Vallejos, Sonia,Erben, Mauricio F.,Ge, Mao-Fa,et al. Conformational Behavior of CH3OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2010,114(10):3703-3712.
APA Torrico-Vallejos, Sonia,Erben, Mauricio F.,Ge, Mao-Fa,Willner, Helge,&Della Vedova, Carlos O..(2010).Conformational Behavior of CH3OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study.JOURNAL OF PHYSICAL CHEMISTRY A,114(10),3703-3712.
MLA Torrico-Vallejos, Sonia,et al."Conformational Behavior of CH3OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study".JOURNAL OF PHYSICAL CHEMISTRY A 114.10(2010):3703-3712.
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