硫族元素
化学
等结构
结晶学
铂金
自然键轨道
键能
吡啶
密度泛函理论
立体化学
分子
计算化学
晶体结构
催化作用
药物化学
有机化学
作者
Anton V. Rozhkov,Eugene A. Katlenok,Margarita V. Zhmykhova,Alexander Yu. Ivanov,Maxim L. Kuznetsov,Nadezhda A. Bokach,Vadim Yu. Kukushkin
摘要
Platinum(II) complexes exhibiting an expressed dz2-nucleophilicity of the positively charged metal centers, namely, [Pt(ppy)(acac)] (1; acacH is acetylacetone; ppyH is 2-Ph-pyridine) and [Pt(ppy)(tmhd)] (2; tmhdH is 2,2,6,6-tetramethylheptanedione-3,5), were cocrystallized with the chalcogen bond donors (4-NC5F4)2Ch (Ch = Se, Te) to form two isostructural cocrystals 1·1/2(4-NC5F4)2Ch, and 2·2/3(4-NC5F4)2Se and 2·(4-NC5F4)2Te. The X-ray data for these cocrystals and appropriate theoretical DFT calculations (PBE0-D3BJ) allowed the recognition of the metal-involving chalcogen bond, namely, Ch···dz2-PtII (its energy spans from −7 to −12 kcal/mol). In 1·1/2(4-NC5F4)2Ch, Ch···dz2-PtII bonding is accompanied by the C···dz2-PtII interaction, representing a three-center bifurcate, whereas in 2·(4-NC5F4)2Te the chalcogen bond Te···dz2-PtII is purely two-centered and is stronger than that in 1·1/2(4-NC5F4)2Ch because of more efficient orbital overlap. The association of 2 with (4-NC5F4)2Te and the structure of the formed adduct in CDCl3 solutions was studied by using 1H, 13C, 19F, 195Pt, 125Te NMR, 19F–1H HOESY, and diffusion NMR methods. The 195Pt and 125Te NMR titration and the isothermal titration calorimetry results revealed a 1:1 association of 2 with (4-NC5F4)2Te.
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