Conformational Behavior of CH3OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study
文献类型：期刊论文
| 作者 | Torrico-Vallejos, Sonia1; Erben, Mauricio F.1; Ge, Mao-Fa2; Willner, Helge3; Della Vedova, Carlos O.1,4 |
| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY A
 |
| 出版日期 | 2010-03-18 |
| 卷号 | 114期号:10页码:3703-3712 |
| ISSN号 | 1089-5639 |
| DOI | 10.1021/jp912044r |
| 英文摘要 | Pure 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. |
| 语种 | 英语 |
| WOS记录号 | WOS:000275327600041 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/71211]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Erben, Mauricio F. |
| 作者单位 | 1.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 |
| 推荐引用方式 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. |
入库方式： OAI收割
来源：化学研究所
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