Interrelation of nonequivalent CC bonds of naphthalene frame and spatial orientation of substituents: Beta-naphthalene sulfonyl fluoride and beta-naphthalene sulfonyl chloride

详细信息    查看全文

• 作者：Nina I. Giricheva^a ; Vjacheslav M. Petrov^a ; Heinz Oberhammer^c ; Valentina N. Petrova^b ; Marwan Dakkouri^d ; Sergey N. Ivanov^a ; Georgiy V. Girichev^b ; ^{g.v.girichev@mail.ru} ; ^{girichev@isuct.ru}
• 关键词：Beta-naphthalene sulfonyl halide ; Molecular structure ; Conformational properties ; Internal rotation ; Enantiomers ; Gas electron diffraction
• 刊名：Journal of Molecular Structure
• 出版年：2013
• 出版时间：24 June, 2013
• 年：2013
• 卷：1042
• 期：Complete
• 页码：66-72
• 全文大小：1227 K

文摘

¦Â-naphthalene sulfonyl fluoride, ¦Â-NaphSF, and ¦Â-naphthalene sulfonyl chloride, ¦Â-NaphSCl, were studied by gas-phase electron diffraction (GED) and quantum chemical calculations (B3LYP and MP2 in combination with cc-pVDZ, aug-cc-pVDZ and cc-pVTZ basis sets). For each compound the calculations predicted the existence of two conformers which are enantiomers. On the basis of the experimental data it was found that the gas phase over ¦Â-NaphSF and NaphSCl at 357(5) K and 395(5) K, respectively, consists of molecular species of C₁ symmetry in which the C_¦ÂSHal plane deviates from the perpendicular orientation relative to the naphthalene skeleton plane. The following geometrical parameters (? and degrees) were obtained from the experiment (uncertainties are in parentheses): r_h1(CH)_aver. = 1.097(7), r_h1(CC)_aver. = 1.410(3), r_h1(CS) = 1.753(6), r_h1(SO)_aver. = 1.414(4), r_h1(SF) = 1.559(5), ¡ÏCC_¦ÂC = 122.8(3), ¡ÏC_¦ÂSF = 103.3(30); ¦µ(C_¦ÁC_¦ÂSF) = 104(6) for ¦Â-NaphSF, and r_h1(CH)_aver. = 1.089(4), r_h1(CC)_aver. = 1.411(3), r_h1(CS) = 1.757(5), r_h1(SO)_aver. = 1.419(3), r_h1(S§³l) = 2.053(4), ¡ÏCC_¦ÂC = 122.8(1), ¡ÏC_¦ÂSCl = 102.2(7), ¦µ(C_¦ÁC_¦ÂSCl) = 108(3) for ¦Â-NaphSCl. The calculated barriers to internal rotation of the sulfonyl halide groups exceed considerably the thermal energy values corresponding to the temperatures of the GED experiments. Natural bond orbital (NBO) analyses of the electron density distribution were applied to explain the peculiarities of the molecular structure of the studied compounds and the deviation from the structures of their benzene analogs.