Lanthanide complexes phosphine oxides

TRUEX [TRansUranium Extraction] A process for removing transuranic elements and lanthanide fission products during the processing of nuclear fuel by solvent extraction. The solvent is a complex phosphine oxide mixed with tributyl phosphate and diluted with n-dodecane. By removing the transuranic elements, the alpha activity of the waste is greatly reduced and the residue is easier to dispose of. Developed by E.P. Horwitz at the Argonne National Laboratory, Chicago, IL. See also SREX, UREX+. 

TRUEX [TRansUranium Extraction] A process for removing transuranic elements and lanthanide fission products during the processing of nuclear fuel by solvent extraction. The solvent is a complex phosphine oxide... 

The discussion of the activation of bonds containing a group 15 element is continued in chapter five. D.K. Wicht and D.S. Glueck discuss the addition of phosphines, R2P-H, phosphites, (R0)2P(=0)H, and phosphine oxides R2P(=0)H to unsaturated substrates. Although the addition of P-H bonds can be sometimes achieved directly, the transition metal-catalyzed reaction is usually faster and may proceed with a different stereochemistry. As in hydrosilylations, palladium and platinum complexes are frequently employed as catalyst precursors for P-H additions to unsaturated hydrocarbons, but (chiral) lanthanide complexes were used with great success for the (enantioselective) addition to heteropolar double bond systems, such as aldehydes and imines whereby pharmaceutically valuable a-hydroxy or a-amino phosphonates were obtained efficiently. 

Charbonniere, L. J. Ziessel, R. Montalti, M. Prodi, L. Zaccheroni, N. Boehme, C. Wipff, G. Luminescent lanthanide complexes of a bis-bipyridine-phosphine-oxide ligand as tools for anion detection. J. Am. Chem. Soc. 2002, 724(26), 7779-7788. 

Other signiflcant complexes of this type, containing one or more lanthanides, are formed by calixarenes (see Calixarenes) Much of this work has been prompted by their potential in separating lanthanides from uranium and other metals. A calixarene ligand with two amide substituents has been synthesised as an extractant for lanthanides dimeric Sm and Eu and monomeric Eu complexes have been prepared. Another calixarene, with four phosphine oxides attached, has been fixed to silica particles and the resulting system has been found to give very efficient extraction of Eu + and Ce + from simulated waste. A calix[4]arene complex of Gd + binds... 

Phosphine Chalcogenides as Ligands. - The complexation of lanthanide and actinide ions by phosphine oxide ligands remains an active area, and a theoretical assessment of the coordination of phosphine oxides (and phosphate esters) by trivalent lanthanide ions has appeared." Trivalent lanthanide complexes of the functionalised enol phosphine oxide (265), (and a related phosphonate), have been describedComplexes of thorium(iv) with bis(di-phenylphosphino) ethane dioxide and bis(diphenylphosphinoyl)amide have also been characterised." Calixarene systems which bear phosphine oxide... 

The coordination properties of phosphine oxides has been explored with late transition-metal (Ru, Co, Rh, Ir, Pd, Pt, Cu, and Au),301 303 305 306 310 316 early transition-metal,317 lanthanide,304,318,319 and actinide307,320 ions. One interesting complex is the palladium(II) complex (148) (Scheme 10) which is an extremely rare example of a ds metal center with a tetrahedral geometry.313 Phosphine oxides have found uses in the extraction of alkali, alkaline earth, and actinide metals in catalysis (hydroformylation of alkenes and epoxides, carbonylation of methanol324) and as a useful crystallization aid (Ph3PO).325... 

CCC (1987) contains a section on sulfoxides, amide, amine oxides, and related ligands that have sections on phosphine oxides and arsine oxides.159 Phosphine and arsine oxide complexes of yttrium and the lanthanides were highlighted in CCC (1987).1 Scandium and yttrium phosphine oxide complexes have been reinvestigated and characterized by multinuclear NMR and X-ray... 

Another lanthanide-based anion sensor 2 exploits a bipyridine phosphine oxide derivative as a pentadentate ligand to coordinate Eu cation. As anions bind to this complex, emission intensity was increased, presumably again due to the displacement of ligated water molecules. 

In this thesis, the control of coordination structures and functionalization of luminescent lanthanide(lll) complexes with LVF hfa and phosphine oxide ligands were investigated. In particular, the author constructed (1) lanthanide coordination polymer with thermostability and thermosensing ability and (2) lanthanide complexes with novel asymmetric coordination structures to improve their emission quantum yields. 

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