Synthesis and crystal and molecular structure of bis(nitrato)[diisopropyl (N,N-diethylcarbamyl)methylenephosphonate]dioxouranium(VI)

Bowen, S.M.; Duesler, Eileen N.; Paine, Robert T.

doi:10.1021/ic00144a018

Cited by 38 publications

(8 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the case of CMPO, although during extraction studies at tracer concentrations of metal ions two CMPO are bound with U(VI), only one is bound in the solid U(VI)-CMPO complex. A similar observation of two neutral donors being bound during solvent extraction and only one in solid complexes of U(VI) with bidentate carbamoylmethylphosphinate and phosphine oxide [48,49] have earlier been reported. In the solid complexes, CMPO and CMP act as a bidentate reagent whereas it acts as monodentate in extraction studies.…”

Section: Characterization Of U(vi) Complexessupporting

confidence: 76%

Extraction of Np(IV), Np(VI), Pu(IV) and U(VI) with Amides, BEHSO and CMPO from Nitric Acid Medium

et al. 1996

View full text Add to dashboard Cite

The extraction of Np(IV), Np(VI), Pu(IV) and U(VI) from a nitric acid medium has been carried out with dibutyldecanamide (DBDA), dihexyldecanamide (DHDA), bis-2-ethylhexylsulphoxide (BEHSO) and octyl(phenyl)-N-N-diisobutyl-carbamoylmethylphosphine oxide (CMPO) using n-dodecane as the diluent. The order of extraction for the metal ions is CMPO> BEHSO>DHDA>DBDA. The species extracted into the organic phase was found to be the disolvate with all the extractante while using hexavalent metal ions Np(VI) and U(VI) and also with tetravalent ions Np(IV) and Pu(IV) in the case of BEHSO and CMPO. However, in the case of DBDA and DHDA, Np(IV) and Pu(IV) were extracted as the trisolvate species. The equilibrium constant (K) for the formation of the above species has been evaluated after applying the possible correction factors. In general, log A" increases with increasing basicity of the extractants. In the case of amides, the plot of log A -verses k H (acid uptake equilibrium constant) gave straight lines which could be represented by the empirical equation : logici) = 5.17 k H + 0.18 and log = 3.11 k H + 1.81 for the respective metal ions. With the help of these empirical equations it is possible to predict the equilibrium constant values of amide complexes of U(VI) or Pu(IV) if the k H values of amides are known. The solid complexes of U(VI) with DHDA and CMPO were synthesized and characterized by elemental analysis and IR spectra. Two molecules of DHDA and only one molecule of CMPO are bound with U(VI). The bidentate nature of CMPO in its solid species has been confirmed.

show abstract

Section: Characterization Of U(vi) Complexessupporting

confidence: 76%

Extraction of Np(IV), Np(VI), Pu(IV) and U(VI) with Amides, BEHSO and CMPO from Nitric Acid Medium

et al. 1996

View full text Add to dashboard Cite

show abstract

“…For this reason, the struc tures of f element complexes with known carbamoylme thylphosphoryl compounds have been examined by a num ber of researchers. [5][6][7][8][9][10][11][12][13] For instance, in the study of the complexation between the phosphonates (RO) 2 P(O)CH 2 C(O)NEt 2 (L, R = Et and Pr i ) and f elements, the complexes UO 2 (L)(NO 3 ) 2 , 6 Th(L) 2 (NO 3 ) 4 , 7 Ln(L) 2 (NO 3 ) 3 (Ln = La-Gd), 8 and Ln(L) 2 (NO 3 ) 3 •H 2 O (Ln = Tb-Eu) 8 were isolated and characterized by spectroscopic methods or, in a number of cases, by a single crystal X ray diffraction. In the complex es of the first three types, the ligand is coordinated via O,O bidentate fashion, while in the last type, the Ln atom is coordinated to the ligand through the phosphoryl O atom and the carbonyl O atom is hydrogen bonded to the water molecule coordinated by the metal atom.…”

mentioning

confidence: 99%

Complexation of N-alkyl(aryl)- and N,N-dialkylcarbamoylmethylphosphine oxides with the f-elements

et al. 2008

View full text Add to dashboard Cite

Complexation of N alkyl(aryl)carbamoylmethylphosphine oxides (CMPO) and their N,N dialkyl analogs in neutral media was studied. N Alkyl derivatives react with praseodymium and europium nitrates both in solution and in the individual state to give 1 : 2 and 1 : 3 complex es, depending on the ratio of the starting reagents; for N aryl amides, 1 : 3 complexes were obtained only. With the uranyl cation, both N alkyl and N,N dialkyl derivatives of CMPO form various 1 : 1 complexes.Phosphorylacetamides, which are also referred to as carbamoylmethylphosphoryl compounds, are neutral or ganophosphorus complexing agents used in disposal of liq uid radioactive wastes. 1-4 Although complexes obtained in model experiments in neutral media often differ from com plexes produced in an organic phase during real extraction from acidic media, it is obvious that the design of more efficient extractants is impossible without an insight into the fundamental coordination chemistry of ligands em ployed in extraction systems. For this reason, the struc tures of f element complexes with known carbamoylme thylphosphoryl compounds have been examined by a num ber of researchers. 5-13For instance, in the study of the complexation between the phosphonates (RO) 2 P(O)CH 2 C(O)NEt 2 (L, R = Et and Pr i ) and f elements, the complexes UO 2 (L)(NO 3 ) 2 , 6 Th(L) 2 (NO 3 ) 4 , 7 Ln(L) 2 (NO 3 ) 3 (Ln = La-Gd), 8 and Ln(L) 2 (NO 3 ) 3 •H 2 O (Ln = Tb-Eu) 8 were isolated and characterized by spectroscopic methods or, in a number of cases, by a single crystal X ray diffraction. In the complex es of the first three types, the ligand is coordinated via O,O bidentate fashion, while in the last type, the Ln atom is coordinated to the ligand through the phosphoryl O atom and the carbonyl O atom is hydrogen bonded to the water molecule coordinated by the metal atom. 8 Ac cording to X ray diffraction data, N,N dimethyldiethoxy phosphorylacetamide (L = (EtO) 2 P(O)CH 2 C(O)NMe 2 ) also forms the lanthanide complexes Ln(L) 2 (NO 3 ) 3 (Ln = La, Sm, Yb, Er, Ce, Eu, and Gd) with bidentate coordination of the O atoms of the phosphoryl and carbo nyl groups. 9 Complexes of the uranyl cation with this ligand and its diphenylphosphoryl analog have a similar structure and a metal to ligand ratio of 1 : 1 (UO 2 (L)(NO 3 ) 2 ). 10

show abstract

“…A previous work suggested that in solution CMPO like [2] and CMPO in more recent works [3,4] act as bidentate extractants in a 1:1 ratio. In solid state, several structural studies concerning CMPO like-uranyl complexes show a ratio 1:1 [5-8].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine dioxouranium nitrate, C48H84N6O20P2U2

Cherfa

Pécaut²,

Nierlich

1999

Zeitschrift Für Kristallographie - New Crystal Structures

View full text Add to dashboard Cite

C48H84N6O20P2U2, orthorhombic, Pna2\ (No. 33), a = 19.7821(3) Ä, b = 10.6352(2) Ä, c = 31.4217(4) Ä, V = 6610.7 Ä 3 , Ζ = 4, Rgt(F) =0.062, wR(F 2 ) = 0.148, Γ= 243 K. Source of materialThe complexe was prepared by addition of 0.8 mmol of CMPO to 1 mmol ofU0 2 (N0 3 )2 · 6H 2 0 in ethanol and chloroforme (V/V). The mixture was heated at 343 Κ during one hour. Crystals were grown by slow evaporation from this solution. Analytically found: %C = 34.6, %N = 4.7, %H = 4.9; calculated: %C = 35.9, %N = 5.2, %H = 5.2. DiscussionThe carbamoyl methyl phosphine oxide derivatives represent an important class of ligands for the TRUEX (Trans Uranium Extraction) process : it removes both the actinide and lanthanide elements from strongly acidic nuclear waste solutions [1], The ligand used in this process is the octyl(phenyl)-./V,jV-diisobutylcarbamoylmethylphosphine oxide, called CMPO: its properties are similar to the other CMPO which are subsequently called CMPO like. A previous work suggested that in solution CMPO like [2] and CMPO in more recent works [3,4] act as bidentate extractants in a 1:1 ratio. In solid state, several structural studies concerning CMPO like-uranyl complexes show a ratio 1:1 [5-8].However only one study concerns a CMPO like : uranyl 2:1 ratio [9] in which the CMPO like act as monodentate ligand. The structure of the free CMPO was reported by Rogers [10]. We report here the first structure involving the CMPO and the uranyl nitrate. The structure contains two independant but similar molecules in the asymmetric unit. A view of one of these is shown in the figure together with the atomic numbering. Η atoms were not indroduced. The linear uranyl group is equatorially surrounded by six oxygen atoms provided by two adjacent and bidentate nitrates and one bidentate CMPO with a cis orientation of the C-0 and P-O groups. The six equatorial oxygen form a nearly planar hexagon (+0.08 Ä) around the U atom. In the structure of the free CMPO [10], the carbonyl and the phosphoryl groups are trans to each other whereas in the uranyl complex they are cis orientated. Rogers compares the C-0 and P-O bond distance in the complexed and uncomplexed CMPO like: they are significantly shorter for the uncomplexed ligand. It is confirmed for the CMPO: 1.232(7) Ä and 1.478(3) Ä for the C-O and P-O bond distances in the free CMPO and 1.31(8) Ä and 1.53(5) Ä in the complexed CMPO.

show abstract

Synthesis and crystal and molecular structure of bis(nitrato)[diisopropyl (N,N-diethylcarbamyl)methylenephosphonate]dioxouranium(VI)

Cited by 38 publications

References 3 publications

Extraction of Np(IV), Np(VI), Pu(IV) and U(VI) with Amides, BEHSO and CMPO from Nitric Acid Medium

Extraction of Np(IV), Np(VI), Pu(IV) and U(VI) with Amides, BEHSO and CMPO from Nitric Acid Medium

Complexation of N-alkyl(aryl)- and N,N-dialkylcarbamoylmethylphosphine oxides with the f-elements

Crystal structure of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine dioxouranium nitrate, C48H84N6O20P2U2

Contact Info

Product

Resources

About