Highly Fluorous Complexes of Ruthenium and Osmium and Their Solubility in Supercritical Carbon Dioxide
作者:Bradley M. Berven、George A. Koutsantonis、Brian W. Skelton、Robert D. Trengove、Allan H. White
DOI:10.1021/ic901880f
日期:2009.12.21
series of ruthenium and osmiumcomplexes containing highly fluorous diphosphine ligands FP∧PF = (F13C6C6H4-p)2P(CH2)2P(p-C6H4C6F13)2 (dfppe) and (F13C6C6H4-p)2P(CH2)3P(p-C6H4C6F13)2 (dfppp) has been prepared. The fluorous diphosphine ligands incorporate four C6F13 “fluoro-ponytails”, and these have been effective in solubilizing the complexes in supercritical carbondioxide (scCO2). Precise solubility
含有高度氟二膦系列钌和锇配合物配体的˚F P ∧ P ˚F =(F 13 Ç 6 Ç 6 ħ 4 - p)2 P(CH 2)2 P(p -C 6 H ^ 4 Ç 6 ˚F 13)2(dfppe)和(F 13 C 6 C 6 H 4 - p)2 P(CH 2)3 P(p已经制备了-C 6 H 4 C 6 F 13)2(dfppp)。氟二膦配体包含四个C 6 F 13 “氟马尾”,并且这些已有效地将络合物溶解在超临界二氧化碳(scCO 2)中。对某些配合物在scCO 2中进行了精确的溶解度测量。新的配合物[MX 2(˚F P ∧ P ˚F)2 ]和[MX(˚F P ∧ P ˚F)(η-C 5 H ^ 5)],M = Ru,Os,X = Cl,Br,已通过多种光谱技术进行了表征,并对其电化学性能进行了测量,其中三种钌配合物也通过单晶X射线研究进行了表征。在X射线结构中观察到的非共价相互作用已通过
Phosphorus(III) ligands with fluorous ponytails
作者:Pravat Bhattacharyya、David Gudmunsen、Eric G. Hope、Ray D. W. Kemmitt、Danny R. Paige、Alison M. Stuart
DOI:10.1039/a704872f
日期:——
A series of phosphorus(III) compounds incorporating one or more C6F13 ‘ponytails’ have been prepared as a pool of ligands for coordination and catalytic studies under the fluorous biphase regime. Solubility studies indicate that only ligands with three or more ponytails are preferentially soluble in perfluorocarbon solvents.
Platinum group metal complexes of a bis(diphenylphosphino)ethane ligand containing perfluoroalkyl ponytails
作者:Eric G. Hope、Raymond D. W. Kemmitt、Alison M. Stuart
DOI:10.1039/a805560b
日期:——
The perfluoroalkyl-derivatised bidentate phosphine (4-F13C6C6H4)2PCH2CH2P(C6H4C6F13-4)2 reacted with [PtCl2(MeCN)2], [PdCl2(MeCN)2] or [RhCl(COD)}2] to yield the complexes [PtCl2(L–L)] 1, [PdCl2(L–L)] 2 and [Pd(L–L)2]2+2Cl– 3 or [RhCl(L–L)}2] 5 respectively. Complex 3 was reduced with NaBH4 to [Pd(L–L)2] 4 and the chloride bridges in 5 were cleaved with triphenylphosphine to yield [RhCl(L–L)(PPh3)] 6. The reaction of the ligand with [RhCl2(η5-C5Me5)}2] in a 1∶1 or a 2∶1 ratio yielded either [RhCl2(η5-C5Me5)}2(L–L)] 7 or, after metathesis with NH4BF4 in acetone, [RhCl(η5-C5Me5)(L–L)]+BF4– 8 respectively. Throughout, spectroscopic studies indicated that the ligand co-ordinates in a similar fashion to bis(diphenylphosphino)ethane (dppe). Complex 7 and the analogous dppe complex are fluxional at room temperature. At the low temperature limit, all the nuclei within these molecules are chemically inequivalent for which simulation suggests a gauche-eclipsed conformation around the PCH2–CH2P bond. Solubility studies indicated that only 4 and 5 are preferentially soluble in perfluorocarbon solvents.
Phosphorus(III) ligands in fluorous biphase catalysis
作者:Pravat Bhattacharyya、Ben Croxtall、Joanne Fawcett、John Fawcett、David Gudmunsen、Eric G Hope、Ray D.W Kemmitt、Danny R Paige、David R Russell、Alison M Stuart、Dan R.W Wood
DOI:10.1016/s0022-1139(99)00166-9
日期:2000.2
The synthesis, coordination chemistry and catalytic applications of a series of perfluoroalkyl-substituted phosphorus(III) ligands is illustrated.