The Key Laboratory for Special Functional Materials, Ministry of Education, Henan University, Kaifeng, 475-004, China.
Inorg Chem. 2012 Oct 15;51(20):10996-1006. doi: 10.1021/ic3014893. Epub 2012 Sep 26.
Utilizing bulky bidentate ligand systems with C(2)F(5) and n-C(3)F(7) groups, antiapicophilic arsoranes (5b and 5c, respectively) were synthesized. A kinetic study on the isomerization of these arsoranes to their more stable isomers showed that the barriers increased in the order of CF(3) < C(2)F(5) < n-C(3)F(7) in accord with their steric bulk. It was also revealed that the degree of freezing isomerization was larger for the change from CF(3) to C(2)F(5) than from C(2)F(5) to n-C(3)F(7), obvious from the differences in activation free energy at 363 K of 1.6 and 0.3 kcal mol(-1), respectively. X-ray structural analysis of several precursors of these two systems disclosed the unique structures of these compounds.
利用具有 C(2)F(5)和 n-C(3)F(7)基团的庞大双齿配体系统，合成了反亲脂性砷烷（分别为 5b 和 5c）。对这些砷烷异构化为更稳定异构体的动力学研究表明，与它们的空间位阻相比，CF(3) < C(2)F(5) < n-C(3)F(7)的顺序增加了障碍。还表明，从 CF(3)到 C(2)F(5)的异构化冻结程度大于从 C(2)F(5)到 n-C(3)F(7)的异构化冻结程度，这从 363 K 时活化自由能的差异明显看出，分别为 1.6 和 0.3 kcal mol(-1)。这些两个系统的几个前体的 X 射线结构分析揭示了这些化合物的独特结构。
