TY - JOUR
T1 - Synthesis and coordination chemistry of phosphine oxide decorated dibenzofuran platforms
AU - Rosario-Amorin, Daniel
AU - Duesler, Eileen N.
AU - Paine, Robert T.
AU - Hay, Benjamin P.
AU - Delmau, Lætitia H.
AU - Reilly, Sean D.
AU - Gaunt, Andrew J.
AU - Scott, Brian L.
PY - 2012/6/18
Y1 - 2012/6/18
N2 - 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 3OH and 5, the 1:1 complexes [In(4)(NO 3) 3], [Pr(4)(NO 3) 3(CH 3CN)] ·0.5CH 3CN, [Er(4)(NO 3) 3(CH 3CN)]·CH 3CN, [Pu(4)Cl 4]·THF and the 2:1 complex [Nd(4) 2(NO 3) 2] 2(NO 3) 2· (H 2O)·4(CH 3OH) 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](NO 3)·4(CH 3OH)} 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.
AB - 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 3OH and 5, the 1:1 complexes [In(4)(NO 3) 3], [Pr(4)(NO 3) 3(CH 3CN)] ·0.5CH 3CN, [Er(4)(NO 3) 3(CH 3CN)]·CH 3CN, [Pu(4)Cl 4]·THF and the 2:1 complex [Nd(4) 2(NO 3) 2] 2(NO 3) 2· (H 2O)·4(CH 3OH) 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](NO 3)·4(CH 3OH)} 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.
UR - http://www.scopus.com/inward/record.url?scp=84862523160&partnerID=8YFLogxK
U2 - 10.1021/ic300301d
DO - 10.1021/ic300301d
M3 - Article
C2 - 22676334
AN - SCOPUS:84862523160
SN - 0020-1669
VL - 51
SP - 6667
EP - 6681
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 12
ER -