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

doi:10.1021/jp912044r

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	Conformational Behavior of CH3OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study
	Torrico-Vallejos, Sonia 1; Erben, Mauricio F.1; Ge, Mao-Fa 2; Willner, Helge 3; Della Vedova, Carlos O.1,4
刊名	JOURNAL OF PHYSICAL CHEMISTRY A
	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
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000275327600041
内容类型	期刊论文
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.