Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
Inorg Chem. 2012 Jun 18;51(12):6667-81. doi: 10.1021/ic300301d. Epub 2012 Jun 7.
A four-step synthesis for 4,6-bis(diphenylphosphinoylmethyl)dibenzofuran (4) from dibenzofuran and a two-step synthesis for 4,6-bis(diphenylphosphinoyl)dibenzofuran (5) are reported along with coordination chemistry of 4 with In(III), La(III), Pr(III), Nd(III), Er(III), and Pu(IV) and of 5 with Er(III). Crystal structure determinations for the ligands, 4·CH(3)OH and 5, the 1:1 complexes [In(4)(NO(3))(3)], [Pr(4)(NO(3))(3)(CH(3)CN)]·0.5CH(3)CN, [Er(4)(NO(3))(3)(CH(3)CN)]·CH(3)CN, [Pu(4)Cl(4)]·THF and the 2:1 complex Nd(4)(2)(NO(3))(2)(NO(3))(2)·(H(2)O)·4(CH(3)OH) are described. In these complexes, ligand 4 coordinates in a bidentate POP'O' mode via the two phosphine oxide O-atoms. The dibenzofuran ring O-atom points toward the central metal cations, but in every case it is more than 4 Å from the metal. A similar bidentate POP'O' chelate structure is formed between 5 and Er(III) in the complex, {Er(5)(2)(NO(3))(2)·4(CH(3)OH)}(0.5), although the nonbonded Er···O(furan) distance is reduced to ∼3.6 Å. The observed bidentate chelation modes for 4 and 5 are consistent with results from molecular mechanics computations. The solvent extraction performance of 4 and 5 in 1,2-dichloroethane for Eu(III) and Am(III) in nitric acid solutions is described and compared against the extraction behavior of n-octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (OΦDiBCMPO) measured under identical conditions.
从苯并呋喃出发，我们报道了 4,6-双（二苯膦酰基甲基）二苯并呋喃（4）的四步合成法和 4,6-双（二苯膦酰基）二苯并呋喃（5）的两步合成法，以及 4 与 In(III)、La(III)、Pr(III)、Nd(III)、Er(III)和 Pu(IV)和 5 与 Er(III)的配位化学。配体 4·CH(3)OH 和 5、1:1 配合物 [In(4)(NO(3))(3)]、[Pr(4)(NO(3))(3)(CH(3)CN)]·0.5CH(3)CN、[Er(4)(NO(3))(3)(CH(3)CN)]·CH(3)CN、[Pu(4)Cl(4)]·THF 和 2:1 配合物 Nd(4)(2)(NO(3))(2)(NO(3))(2)·(H(2)O)·4(CH(3)OH) 的晶体结构测定结果都已报道。在这些配合物中，配体 4 通过两个膦氧原子以双齿 POP'O'模式配位。苯并呋喃环上的 O-原子指向中心金属阳离子，但在每种情况下，它与金属的距离都超过 4 Å。在配合物中，5 和 Er(III)之间也形成了类似的双齿 POP'O'螯合结构，{Er(5)(2)(NO(3))(2)·4(CH(3)OH)}(0.5)，尽管非键合的 Er···O(呋喃)距离缩短至约 3.6 Å。4 和 5 的观察到的双齿螯合模式与分子力学计算的结果一致。还描述并比较了 4 和 5 在 1,2-二氯乙烷中对硝酸溶液中的 Eu(III)和 Am(III)的溶剂萃取性能，与在相同条件下测量的正辛基（苯基）-N,N-二异丁基碳酰甲基膦氧化物（OΦDiBCMPO）的萃取行为进行了比较。
