Complexation of the uranyl ion (UO2)2+ with a tetraphenylimidodiphosphinate ligand: the first trinuclear uranyl complex comprising a double μ2-oxo (UO2) bridge

Cea‐Olivares, Raymundo; Canseco-Melchor, Graciela; Moya‐Cabrera, Mónica; Garcı́a-Montalvo, Verónica; Alvarado‐Rodríguez, José G.; Toscano, Rubén A.

doi:10.1016/j.inoche.2004.12.010

Cited by 10 publications

(7 citation statements)

References 12 publications

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“…The 100 K crystal structure of 7 was determined (see ESI †) and established to be similar to the previously determined 293 K crystal structure, 32 except that half a hexane solvent molecule per trimer was found.…”

Section: Crystal Structure Of [Uo2(tpip)2] 3 (7)05(c 6 H 14 )mentioning

confidence: 63%

“…Both of these monomeric complexes were characterised in solution and in the solid state. Interestingly, repetition of the reaction described by Cea-Olivares et al, 32 but by addition of Na[TPIP] to uranyl nitrate afforded, after isolation and recrystallisation, a previously unreported bimetallic complex [UO 2 (TPIP) 2 ] 2 (6) and a small amount of the trimetallic complex [UO 2 (TPIP) 2 ] 3 (7). Again, both of these complexes were characterised in the solid state and in solution.…”

Section: Synthesis Of Uranyl(vi) Tetraimidodiphosphinate (Tpip) Compl...mentioning

confidence: 86%

“…In light of the above, we extended our study to a related monoanionic bidentate ligand tetraphenylimidodiphosphine (TPIP) which is able to yield discrete multimetallic complexes with uranyl(VI) 32 and will enable us to correlate the number of uranyl units in a molecule with the emission profiles. The anion of TPIP, [(Ph 2 PO) 2 N]possesses the correct electronic structure to render this study tractable, since the charge of the ligand is mainly localised on the amido nitrogen atom (cf .…”

Section: Synthesis Of Uranyl(vi) Tetraimidodiphosphinate (Tpip) Compl...mentioning

confidence: 99%

“…34 The anion of tetraphenylimidophosphine [(Ph 2 PO) 2 N] -(TPIP) appears to promote the interesting and rather rare property of a {UO 2 } 2+ -{UO 2 } 2+ uranium-oxo-uranium interaction in the trimetallic [UO 2 (TPIP) 2 ] 3 . 32 In this compound, the uranyl units are orthogonally connected via dative bonding of a Lewis basic uranyl oxygen to a neighbouring Lewis acidic metal centre (Scheme 2). These interactions can also be viewed as oxo bridges or 'cationcation' interactions (vide infra) where the basicity of the oxo ligands may be a result of competition between the oxo ligands or charge repulsion of the uranyl units possessing different degrees of Lewis acidity.…”

Section: Synthesis Of Uranyl(vi) Tetraimidodiphosphinate (Tpip) Compl...mentioning

confidence: 99%

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Probing the local coordination environment and nuclearity of uranyl(vi) complexes in non-aqueous media by emission spectroscopy

et al. 2011

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We describe the synthesis, solid state and solution properties of two families of uranyl(VI) complexes that are ligated by neutral monodentate and anionic bidentate P=O, P=NH and As=O ligands bearing pendent phenyl chromophores. The uranyl(VI) ions in these complexes possess long-lived photoluminescent LMCT (3)Π(u) excited states, which can be exploited as a sensitive probe of electronic structure, bonding and aggregation behaviour in non-aqueous media. For a family of well defined complexes of given symmetry in trans-[UO(2)Cl(2)(L(2))] (L = Ph(3)PO (1), Ph(3)AsO (2) and Ph(3)PNH (3)), the emission spectral profiles in CH(2)Cl(2) are indicative of the strength of the donor atoms bound in the equatorial plane and the uranyl bond strength; the uranyl LMCT emission maxima are shifted to lower energy as the donor strength of L increases. The luminescence lifetimes in fluid solution mirror these observations (0.87-3.46 μs) and are particularly sensitive to vibrational and bimolecular deactivation. In a family of structurally well defined complexes of the related anion, tetraphenylimidodiphosphinate (TPIP), monometallic complexes, [UO(2)(TPIP)(thf)] (4), [UO(2)(TPIP)(Cy(3)PO)] 5), a bimetallic complex [UO(2)(TPIP)(2)](2) (6) and a previously known trimetallic complex, [UO(2)(TPIP)(2)](3) (7) can be isolated by variation of the synthetic procedure. Complex 7 differs from 6 as the central uranyl ion in 7 is orthogonally connected to the two peripheral ones via uranyl → uranium dative bonds. Each of these oligomers exhibits a characteristic optical fingerprint, where the emission maxima, the spectral shape and temporal decay profiles are unique for each structural form. Notably, excited state intermetallic quenching in the trimetallic complex 7 considerably reduces the luminescence lifetime with respect to the monometallic counterpart 5 (from 2.00 μs to 1.04 μs). This study demonstrates that time resolved and multi-parametric luminescence can be of value in ascertaining solution and structural forms of discrete uranyl(VI) complexes in non-aqueous solution.

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Section: Crystal Structure Of [Uo2(tpip)2] 3 (7)05(c 6 H 14 )mentioning

confidence: 63%

Section: Synthesis Of Uranyl(vi) Tetraimidodiphosphinate (Tpip) Compl...mentioning

confidence: 86%

Section: Synthesis Of Uranyl(vi) Tetraimidodiphosphinate (Tpip) Compl...mentioning

confidence: 99%

Section: Synthesis Of Uranyl(vi) Tetraimidodiphosphinate (Tpip) Compl...mentioning

confidence: 99%

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Probing the local coordination environment and nuclearity of uranyl(vi) complexes in non-aqueous media by emission spectroscopy

et al. 2011

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“…The ligand K[(OPPh 2 ) 2 N] reacts with [UO 2 (NO 3 ) 2 ] to give the trimeric complex [(UO 2 {(OPPh 2 ) 2 N} 2 ) 3 ], which was isolated and structurally characterised (Figure 8). 57 In this trimer the central uranyl atom is bound to the two other atoms by means of CCIs with only small distortions of the UO bond lengths. A recent photoluminescence study on this trimer strongly suggests that it persists in solution.…”

Section: Supramolecular Chemistrymentioning

confidence: 99%

New Reactivity of the Uranyl(VI) Ion

Baker

2012

Chemistry A European J

105

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The chemistry of the uranyl ion ([UO(2)](2+)) has evolved remarkably over the past few years, with unexpected reactivity observed that challenge our understanding of this ion, and of actinides in general. This review highlights some recent advances in the field, focussing on the organometallic chemistry of the uranyl moiety, which is not well developed in comparison to lower oxidation states of uranium. The use of uranyl as a catalyst is highlighted and the newly developed supramolecular chemistry is described. The uranyl oxygen atoms have been considered as inert, but recent work has shown that is not necessarily the case and is discussed herein. Finally, reduction to the [UO(2)](+) ion will be discussed.

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Dichalcogenoimidodiphosph(in)ate Ligands

Haiduc

2013

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering

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Complexation of the uranyl ion (UO2)2+ with a tetraphenylimidodiphosphinate ligand: the first trinuclear uranyl complex comprising a double μ2-oxo (UO2) bridge

Cited by 10 publications

References 12 publications

Probing the local coordination environment and nuclearity of uranyl(vi) complexes in non-aqueous media by emission spectroscopy

Probing the local coordination environment and nuclearity of uranyl(vi) complexes in non-aqueous media by emission spectroscopy

New Reactivity of the Uranyl(VI) Ion

Dichalcogenoimidodiphosph(in)ate Ligands

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