Synthesis and Coordination Chemistry of Phosphine Oxide Decorated Dibenzofuran Platforms
详细信息 查看全文
- 作者：Daniel Rosario-Amorin ; Eileen N. Duesler ; Robert T. Paine ; Benjamin P. Hay ; L忙titia H. Delmau ; Sean D. Reilly ; Andrew J. Gaunt ; Brian L. Scott
- 刊名：Inorganic Chemistry
- 出版年：2012
- 出版时间：June 18, 2012
- 年：2012
- 卷：51
- 期：12
- 页码：6667-6681
- 全文大小：678K
- 年卷期：v.51,no.12(June 18, 2012)
- ISSN：1520-510X
文摘
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路CH3OH and 5, the 1:1 complexes [In(4)(NO3)3], [Pr(4)(NO3)3(CH3CN)]路0.5CH3CN, [Er(4)(NO3)3(CH3CN)]路CH3CN, [Pu(4)Cl4]路THF and the 2:1 complex [Nd(4)2(NO3)2]2(NO3)2路(H2O)路4(CH3OH) are described. In these complexes, ligand 4 coordinates in a bidentate POP鈥睴鈥?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 脜 from the metal. A similar bidentate POP鈥睴鈥?chelate structure is formed between 5 and Er(III) in the complex, {[Er(5)2(NO3)2](NO3)路4(CH3OH)}0.5, although the nonbonded Er路路路Ofuran distance is reduced to 3.6 脜. 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 (O桅DiBCMPO) measured under identical conditions.