Strenalyuk Tatyana, Samdal Svein, Volden Hans Vidar
Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, NO-0315 Oslo, Norway.
J Phys Chem A. 2008 Sep 25;112(38):9075-82. doi: 10.1021/jp804105d. Epub 2008 Aug 28.
The molecular structures of chloro(phthalocyaninato)aluminum(III) (ClPcAl) and chloro(phthalocyaninato)gallium(III) (ClPcGa) have been determined by using the gas electron diffraction (GED) method and augmented by quantum chemical calculations. The molecular structures of fluoro(phthalocyaninato)aluminum(III) (FPcAl), fluoro(phthalocyaninato) gallium(III) (FPcGa), chloro(tetrakis(1,2,5-thiadiazole)porphyrazinato)aluminum(III) (ClTTDPzAl), and chloro(tetrakis(1,2,5-thiadiazole)porphyrazinato)gallium(III) (ClTTDPzGa) have been optimized at the level B3LYP with basis sets 6-31G*, 6-311++G**, and cc-pVTZ, and the structures have been compared with those obtained by X-ray diffraction. Vibrational frequencies have been calculated for all six molecules at all basis sets combinations, except B3LYP/cc-pVTZ. These calculations predict that all molecules have C 4 v symmetry with the metal atom above the plane defined by the four inner cavity N atoms and an almost planar macrocycle. The most important structure parameters (GED|B3LYP/cc-pVTZ) are h (height of the metal atom above the inner cavity) h = 50.3(32)|44.9 pm, r(Al-Cl) = 214.5(16)|217.4 pm, r(Al-N) = 197.6(9)|198.7 pm, angle(Cl-Al-N) = 104.8(9)|103.1 degrees, angle(Al-N-C) = 124.2(7)|125.9 degrees for ClPcAl, and the corresponding values for ClPcGa are h = 53.1(28)|50.2 pm, r(Ga-Cl) = 218.9(14)|222.3 pm, r(Ga-N) = 200.6(8)|202.6 pm, angle(Cl-Ga-N) = 105.4(8)|104.3 degrees, angle(Ga-N-C) = 123.8(8)|125.0 degrees. Parenthesized values are estimated error limits defined as 2.5(sigma(2)(lsq) + (0.001 x r)(2))(1/2) for distances and 2.5sigma(lsq) for angles. The title compounds are all flexible molecules with about five vibrational frequencies below 100 cm(-1).
通过气体电子衍射（GED）方法测定了氯（酞菁）铝（III）（ClPcAl）和氯（酞菁）镓（III）（ClPcGa）的分子结构，并通过量子化学计算进行了补充。在B3LYP水平上，使用基组6 - 31G*、6 - 311++G**和cc - pVTZ对氟（酞菁）铝（III）（FPcAl）、氟（酞菁）镓（III）（FPcGa）、氯（四（1,2,5 - 噻二唑）卟啉）铝（III）（ClTTDPzAl）和氯（四（1,2,5 - 噻二唑）卟啉）镓（III）（ClTTDPzGa）的分子结构进行了优化，并将这些结构与通过X射线衍射获得的结构进行了比较。除了B3LYP/cc - pVTZ组合外，对所有六个分子在所有基组组合下都计算了振动频率。这些计算预测所有分子都具有C₄ᵥ对称性，金属原子位于由四个内腔N原子定义的平面上方，大环几乎呈平面状。最重要的结构参数（GED|B3LYP/cc - pVTZ）对于ClPcAl为：h（金属原子在内腔上方的高度）h = 50.3(32)|44.9 pm，r(Al - Cl) = 214.5(16)|217.4 pm，r(Al - N) = 197.6(9)|198.7 pm，∠(Cl - Al - N) = 104.8(9)|103.1°，∠(Al - N - C) = 124.2(7)|125.9°；对于ClPcGa的相应值为：h = 53.1(28)|50.2 pm，r(Ga - Cl) = 218.9(14)|222.3 pm，r(Ga - N) =
