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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >1-PHENYL-1,2-DICARBA-CLOSO-DODECABORANE, 1-PH-1,2-CLOSO-C2B10H11 - SYNTHESIS, CHARACTERIZATION, AND STRUCTURE AS DETERMINED IN THE GAS PHASE BY ELECTRON DIFFRACTION, IN THE CRYSTALLINE PHASE AT 199 K BY X-RAY DIFFRACTION, AND BY AB INITIO COMPUTATION
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1-PHENYL-1,2-DICARBA-CLOSO-DODECABORANE, 1-PH-1,2-CLOSO-C2B10H11 - SYNTHESIS, CHARACTERIZATION, AND STRUCTURE AS DETERMINED IN THE GAS PHASE BY ELECTRON DIFFRACTION, IN THE CRYSTALLINE PHASE AT 199 K BY X-RAY DIFFRACTION, AND BY AB INITIO COMPUTATION

机译：1-苯-1,2-二碳杂-十二烷基硼烷，1-PH-1,2-CLOSO-C2B10H11-电子衍射在气相中确定的合成，表征和结构，在199 K晶相中X射线衍射和从头算

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摘要

The compound 1-phenyl-1,2-dicarba-closo-dodecaborane(12), 1-C6H5-1,2-closo-C2B10H11 (1), has been synthesized and characterized by a complete assignment of its B-11 NMR spectrum via B-11(H-1)/B-11{H-1} (COSY), H-1{B-11(selective)} and H-1{B-11}/H-1{B-11} (COSY) spectroscopy. An electron- and X-ray diffraction investigation of 1, complemented by ab initio calculations, has been undertaken. The gas-phase electron-diffraction (GED) data can be fitted by several models describing conformations which differ in the position of the phenyl ring with respect to the carborane cage. Local symmetries of C-2v and D-6h for the 1,2-C2B10 and C-6 moieties, respectively, were adopted in the GED model in order to simplify the problem. In addition, constraints among the close-lying C-C and B-B bonds were employed. However, even though such simplifications led to satisfactory refinements (R(G) = 0.069-0.071), a unique, definitive solution could not be gained. The (C-C)(mean), (C-B)(mean), and (B-B)(mean) bond lengths, r(a), are ca. 1.44, 1.72, and 1.78 Angstrom, respectively. The C-6 hexagon, with r(a)(C-C) = ca. 1.394 Angstrom, either eclipses the C(1)-C(2) vector (overall C-s symmetry) or more or less eclipses the C(1)-B(4) cluster bond (overall C-1 symmetry). In contrast, in the solid at 199 K, the ring lies at a position intermediate between the two GED positions, as determined by X-ray crystallography [C8H16B10, monoclinic P2(1)/a: a = 12.047(3) Angstrom, b = 18.627(4) Angstrom, c = 12.332(5) Angstrom, beta = 110.09(4)degrees, Z = 8]. The C-B distances span the range 1.681(6)-1.743(5) Angstrom, and B-B lengths lie between 1.756(6) and 1.795(6) Angstrom. A similar conformation was found for the theoretical (RHF/6-31G* level) structure which was fully optimized in C-1 symmetry. The r(e) distances are consistent with the dimensions derived in the experimental studies. IGLO calculations of the B-11 chemical shifts, in addition to SCF single-point energies of the GED structures, further support these observations. [References: 46]
机译：合成了化合物1-苯基-1,2-二氨基甲酸-双十二硼烷（12）1-C6H5-1,2-氯-C2B10H11（1），并通过完全分配其B-11 NMR光谱进行了表征通过B-11（H-1）/ B-11 {H-1}（COSY），H-1 {B-11（selective）}和H-1 {B-11} / H-1 {B-11 }（COSY）光谱。进行了电子和X射线衍射研究（从头算），补充了从头算。气相电子衍射（GED）数据可以通过几种模型进行拟合，这些模型描述了在苯环相对于碳硼烷笼的位置不同的构象。在GED模型中，分别对1,2-C2B10和C-6部分采用C-2v和D-6h的局部对称性，以简化问题。此外，采用了紧密的C-C和B-B键之间的约束。但是，即使这样的简化导致令人满意的改进（R（G）= 0.069-0.071），也无法获得唯一的确定性解决方案。 （C-C）（平均值），（C-B）（平均值）和（B-B）（平均值）键长r（a）约为。分别为1.44、1.72和1.78埃。 C-6六角形，r（a）（C-C）=ca。 1.394埃，使C（1）-C（2）矢量（整体C-s对称）黯然失色，或或多或少地使C（1）-B（4）簇键（整体C-1对称性）黯然失色。相反，在199 K的固体中，环位于两个GED位置之间的中间位置，这是通过X射线晶体学测定的[C8H16B10，单斜晶P2（1）/ a：a = 12.047（3）埃，b ＝ 18.627（4）埃，c ＝ 12.332（5）埃，β＝ 110.09（4）度，Z ＝ 8]。 C-B距离范围为1.681（6）-1.743（5）埃，B-B长度在1.756（6）和1.795（6）埃之间。对于理论结构（RHF / 6-31G *水平），发现了相似的构型，该构型已完全以C-1对称性优化。 r（e）距离与实验研究中得出的尺寸一致。除了GED结构的SCF单点能量以外，B-11化学位移的IGLO计算还进一步支持了这些观察结果。 [参考：46]

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