Nieto Sonia, Pérez Julio, Riera Lucía, Riera Víctor, Miguel Daniel
Departamento de Química Orgánica e Inorgánica-IUQOEM, Facultad de Química, Universidad de Oviedo-CSIC, 33006 Oviedo, Spain.
Chemistry. 2006 Mar 1;12(8):2244-51. doi: 10.1002/chem.200500913.
The behavior of the receptors [Re(CO)3(Hdmpz)3]BAr'4 (Hdmpz = 3,5-dimethylpyrazole) (1) and [Re(CO)3(HtBupz)3]BAr'4 (HtBupz = 3(5)-tert-butylpyrazole) (2; Ar' = 3,5-bis(trifluoromethyl)phenyl) toward the anions fluoride, chloride, bromide, iodide, hydrogensulfate, dihydrogenphosphate, nitrate, and perrhenate was studied in CD3CN solution. In most cases, the receptors were stable. Anion exchange was fast, and binding constants were calculated from the NMR titration profiles. The structure of the adduct [Re(CO)3(HtBupz)3] x NO3 (3) was determined by X-ray diffraction. Two pyrazole moieties are hydrogen-bonded to one nitrate oxygen atom, and the third pyrazole moiety is hydrogen-bonded to an oxygen atom of an adjacent nitrate, leading to infinite chains. The structure of the adduct [Re(CO)3(Hdmpz)3]BAr'4acetone (4), also determined by X-ray diffraction, showed a similar interaction of two pyrazole N-H groups with the acetone oxygen atom. F- and H2PO4(-) deprotonate the receptors, and HSO4(-) decomposed 1. The structure of one of the decomposition products (5), determined by X-ray diffraction, is consistent with pyrazole protonation and substitution by sulfate.
研究了受体[Re(CO)₃(Hdmpz)₃]BAr'₄（Hdmpz = 3,5 - 二甲基吡唑）（1）和[Re(CO)₃(HtBupz)₃]BAr'₄（HtBupz = 3(5) - 叔丁基吡唑）（2；Ar' = 3,5 - 双（三氟甲基）苯基）在CD₃CN溶液中对氟离子、氯离子、溴离子、碘离子、硫酸氢根离子、磷酸二氢根离子、硝酸根离子和高铼酸根离子的行为。在大多数情况下，受体是稳定的。阴离子交换很快，结合常数由NMR滴定曲线计算得出。通过X射线衍射确定了加合物[Re(CO)₃(HtBupz)₃]×NO₃（3）的结构。两个吡唑部分通过氢键与一个硝酸根氧原子相连，第三个吡唑部分与相邻硝酸根的一个氧原子形成氢键，从而形成无限链。同样通过X射线衍射确定的加合物[Re(CO)₃(Hdmpz)₃]BAr'₄丙酮（4）的结构显示，两个吡唑N - H基团与丙酮氧原子有类似的相互作用。F⁻和H₂PO₄⁻使受体去质子化，HSO₄⁻使1分解。通过X射线衍射确定的一种分解产物（5）的结构与吡唑质子化和被硫酸根取代一致。
