亚磷酸三苯酯臭氧化合物分解产生单重态氧的研究

This letter reports a study on producing gas-phase O2（a1Δ）by decomposition of triphenyl phosphite ozonide（（C6H5O）3 PO3,TPPO3）under a number of reaction conditions. For the first time,the cooperative emission at wavelengths 634 and 703 nm of O2（a1Δ）generated by TPPO3 decomposition are observed. Specifically,under the condition of catalyzed decomposition by pyridine of TPPO3 solution in CFCl3 at low temperature,the emission spectrum is the same as that from the basic hydrogen peroxide plus chlorine reaction. This shows the feasibility of developing a new source for singlet delta oxygen. However,in the experiments of spontaneous decomposition of solid TPPO3 and thermal decomposition of TPPO3 solution on a high temperature surface,the spectra have a wide emission background around the 634 and 703 nm peaks,which indicates the production of some excited species than O2（a1Δ）. Besides,there are about 2%-3% CO and 1. 5%-2% CO2 in the gaseous products together with a small amount of insoluble in acetone solid product,which imply that other than the formation of O2（a1Δ）and TPPO by unimolecular decomposition of TPPO3,more complicated reactions may take place. The study of the reaction mechanism,the optimization of the expertise of O2（a1Δ）generation by TPPO3 decomposition as well as measurement of absolute concentration of O2（a1Δ）are under way.     

Synergic extraction of uranium(VI) by combination of tri-iso-octylamine and neutral donors

Synergistic effect of neutral donors like tri-butyl phosphate (TBP), triphenyl phosphine oxide (TPPO), trioctyl phosphine oxide (TOPO), and dimethyl sulphoxide (DMSO) on the extraction of uranium(VI) by tri-isooctyl amine into CCl₄ is reported. Synergistic coefficients and adduct formation constants are calculated from distribution data and correlated with relative donor abilities of added bases.     

Studies of degradation enhancement of polystyrene by flame retardant additives

Experimental methods as well as thermodynamic modeling techniques were utilized to explore potential gas and condensed-phase contributions of various flame retardant (FR) additives with polystyrene polymer. FR additives investigated include hexabromocyclododecane (HBCD), triphenyl phosphine oxide (TPPO), triphenyl phosphate (TPP), triphenyl phosphine sulfide (TPPS), and sulfur. Flame studies of fundamental FR activity were also employed using molecular beam mass spectrometry analysis of FR active species directly in a flame system. The flame studies show direct evidence for active bromine (HBr, Br) species for HBCD and active phosphorous species (HPO₂, PO, PO₂ HPO₃) species for TPPO and TPP which provide high potential for gas-phase activity for these FR additives. Various experimental measurements were also done to assess the degradation species and the degree of degradation of polystyrene by the FR additives. These studies support enhanced degradation of the base polystyrene polymer by the FR additive as a major pathway for condensed FR activity for HBCD and sulfur FR additives. Phosphorous based structures appear to show little enhancement of polystyrene degradation.     

Thermal behavior of poly(bisphenol A carbonate) in the presence of phosphorus compounds

To clarify the interaction between poly(bisphenol A carbonate) (PBAC) and phosphorus compounds such as triphenylphosphine oxide (TPPO), triphenyl phosphate (TPP), and resorcinol bis(diphenyl phosphate) (RDP), PBAC was heated in the presence of these phosphorus compounds at 240 °C for 2 h, and the resulting polymers were analyzed by ¹H NMR spectroscopy and gel permeation chromatography. When heated in the presence of TPPO, the PBAC sample decomposed extensively, resulting in a substantial decrease in molecular weight. On the other hand, thermal treatment in the presence of the phosphates increased the molecular weight. In both cases the molecular weight distribution became narrower. Thermal treatment of PBAC in the presence of both TPPO and TPP allowed us to control the molecular weight with a narrower distribution. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1069–1074, 2004     

Reactions of triphenyl phosphite with di- and tribromoacetaldehydes

Conclusions The reaction of triphenyl phosphite and di- and tribromoacetaldehydes proceeds through initial halophilic attack with subsequent formation of triphenyl phosphate and tetraphenylphosphonium bromide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1668–1670, July, 1988.     

Synergistic effect of neutral donors on the extraction of zirconium(IV) by salicylaldoxime in dichloromethane

Liquid-liquid extraction of zirconium(IV) was investigated from dilute hydrochloric acid medium by salicyaldoxime (HA) in dichloromethane. The metal was spiked with ⁹⁵Zr and analyzed by its radioactivity. The effects of different donors, like trioctyl phosphine oxide (TOPO), triphenyl phosphine oxide (TPPO), tributyl phosphine oxide (TBPO), tributyl phosphate (TBP), trioctyl amine (TOA) and Amberlite LA-2 were studied. The adduct formation constants for both binary species (metal-ligand) and ternary species (metal-ligand-donor) were also calculated form the distribution data.One of the authors (S.B.) thanks The University of Burdwan for providing senior research fellowship to her. She also wishes to thank Dr. D. Mukherjee and Dr. S. Bhattacharya, B.U. for their valuable suggestions.     

The structural and spectroscopic characterisation of three actinyl complexes with coordinated and uncoordinated perrhenate: [UO2(ReO4)2(TPPO)3], [[(UO2)(TPPO)3]2(mu2-O2)][ReO4]2 and [NpO2(TPPO)4][ReO4

The first structural characterization of an actinide complex with coordinated perrhenate is reported, [UO2(ReO4)2(TPPO)3] (1). In this [UO2]2+ complex two [ReO4]- anions and three TPPO (triphenylphosphine oxide) P=O donor ligands are coordinated in the equatorial plane in a cisoid arrangement. This bonding arrangement, and apparent strain observed in the equatorially bonded ligands, is attributed to the solid state packing in adjacent molecules in which hydrophobic TPPO ligands form an effective "shell" around a hydrophilic core of two UO2(ReO4)2 moieties. Solid state vibrational spectroscopy (infrared and Raman), 31P CP MAS NMR and elemental analysis are also consistent with the formula of 1. Solution state vibrational spectroscopy and 31P NMR measurements in EtOH indicate the lability of the TPPO and [ReO4]- groups. The photolytic generation of peroxide in EtOH solutions of 1 leads to the formation of trace quantities of [[(UO2)(TPPO)3]2(mu2-O2)][ReO4]2, 2, in which the coordinated [ReO4]- groups of 1 have been displaced by bridging O2(2-), derived from atmospheric O2. Finally, attempts to synthesise a [NpO2]+ analogue of have resulted only in the formation of [NpO2(TPPO)4][ReO4], 3, in which [ReO4]- acts solely as a counter anion. From these results it can be concluded that [ReO4]- will bond to [UO2]2+, but will be readily displaced by a more strongly coordinating ligand (e.g. peroxide) and will not coordinate to an actinyl cation with a lower charge, [NpO2]+, under the same reaction conditions.     

Direct and dye-sensitized aqueous photo-oxidation of 3-indoleacetic acid, methyl-3-indoleacetate and 1-methyl-3-indoleacetic acid 1-methyl-3-indoleacetic acid II: Quantum yields and mechamism

Mechanisms accounting for the types and yields of the products obtained in direct and dye-sensitized photo-oxidation of the compounds 3-indoleacetic acid (1a), methyl-3-indoleacetate (1b) and 1-methyl-3-indoleacetic acid (1c) in aqueous buffer (pH 5 or pH 8) containing 10% methanol are discussed. In the direct irradiation at pH 5 of acid 1a and its methyl ester 1b, the first detectable products are the corresponding 3-indolemethanols 6a and 6b, their methyl ethers 7a and 7b, and the dimeric compounds 14a and 14b, in aerobic and anaerobic conditions. The same primary products are detected in dye-sensitized photo-oxidation at pH 5. These results support the primary formation of radicals I and II, and of the peroxy forms III and IV, from which thermal reactions can explain all the products found. In both direct and dye-sensitized photo-oxidation at pH 8, only products from the oxidative cleavage of the indolic 2,3-double bond are observed. In dye-sensitized reactions, the products found are in accordance with the existence of competing type I (through radicals) and type II (through singlet oxygen) photosensitized oxygenation processes, their relative proportions depending on the pH of the medium. In direct irradiation, the same intermediates seem to be formed. Quantum yield values of 1a disappearance also depend on the experimental conditions, the highest value found being 28.5% for the direct irradiation at pH 5.     

Crystal structure and triboluminescence of the [Eu(TTA)2(NO3)(TPPO)2] complex

The crystal structure of [Eu(TTA)₂(NO₃)(TPPO)₂] (I) (TTA = thenoyltrifluoroacetone, TPPO = triphenylphosphine oxide) possessing intense triboluminescence was established by X-ray crystallography. The crystals are triclinic, noncentrocymmetrical: a = 11.047(3) Å, b = 11.794(3) Å, c = 12.537(3) Å; α = 102.635 (4)°, β = 102.088(4)°,γ = 117.765(3)°; space group P1, Z = 1. The central Eu(III) atom coordinates two oxygen atoms of two TPPO molecules at distances of 2.271 Å and 2.282 Å, two oxygen atoms of the nitrate group at distances of 2.478 Å and 2.481 Å, four oxygen atoms of two TTA ions at distances of 2.365 Å, 2.381 Å, and 2.363 Å, 2.371 Å (coordination number is 8). The coordination polyhedron of the Eu(III) atom is a distorted dodecahedron. Possible reasons for spectral differences in the Stark structure of photo-and triboluminescence of I are discussed.     

Crystal structure and triboluminescence of the [Tb(BTFA)2(NO3)(TPPO)2] complex

The crystal structure of the [Tb(BTFA)₂(NO₃)(TPPO)₂] complex (TPPO is triphenylphosphine oxide, BTFA is benzoyltrifluoracetone), which exhibits strong triboluminescence, has been established by X-ray crystallography. The crystals are triclinic: a = 11.668(3) Å, b = 11.700(3) Å, c = 12.512(3) Å, α = 65.161(4°), β = 79.120(4)°, γ = 61.860(4)°, space group P1, Z = 1. The central terbium(III) atom coordinates two oxygen atoms from two triphenylphosphine oxide molecules (Tb-O, 2.264(3) and 2.273(3) Å), two oxygen atoms from the nitrate group (Tb-O, 2.460(3) and 2.476(3) Å), and four oxygen atoms from two benzoyltrifluoroacetonate groups (Tb-O, 2.329(3), 2.399(3), 2.351(3), and 2.367(3) Å). The coordination polyhedron of the Tb(III) atom is a distorted dodecahedron. The photoluminescence and triboluminescence spectra of the [Tb(BTFA)₂(NO₃)(TPPO)₂] complex are identical and caused by the f-f luminescence of Tb³⁺.     

Hybrid EuIII Coordination Luminophore Standing on Two Legs on Silica Nanoparticles for Enhanced Luminescence

In this study, we have demonstrated a two-legged, upright molecular design method for monochromatic and bright red luminescent Ln^III-silica nanomaterials. A novel Eu^III-silica hybrid nanoparticle was developed by using a doubly binding TPPO−Si(OEt)₃ (TPPO: triphenyl phosphine oxide) linker. The TPPO−Si(OEt)₃ was confirmed by ¹H, ³¹P, ²⁹Si NMR spectroscopy and single-crystal X-ray analysis. Luminescent Eu(hfa)₃ and Eu(tfc)₃ moieties (hfa: hexafluoroacetylacetonate, tfc: 3-(trifluoromethylhydroxymethylene)camphorate) were fixed onto TPPO−Si(OEt)₃-modified silica nanoparticles, producing Eu(hfa)₃(TPPO−Si)₂-SiO₂ and Eu(tfc)₃(TPPO−Si)₂-SiO₂, respectively. Eu(hfa)₃(TPPO−Si)₂−SiO₂ exhibited the higher intrinsic luminescence quantum yield (93 %) and longer emission lifetime (0.98 ms), which is much larger than those of previously reported Eu^III-based hybrid materials. Eu(tfc)₃(TPPO−Si)₂−SiO₂ showed an extra-large intrinsic emission quantum yield (54 %), although the emission quantum yield for the precursor Eu(tfc)₃(TPPO−Si(OEt)₃)₂ was found to be 39 %. These results confirmed that the TPPO−Si(OEt)₃ linker is a promising candidate for development of Eu^III-based luminescent materials.     

Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride)

Contrary to a previous report, the sulfurisation of phosphorus(III) derivatives by 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride) does not yield carbon disulfide and cyanamide as the additional reaction products. The reaction of xanthane hydride with triphenyl phosphine or trimethyl phosphite yields triphenyl phosphine sulfide or trimethyl thiophosphate, respectively, and thiocarbamoyl isothiocyanate which has been trapped with nucleophiles. The reaction pathway involves initial nucleophilic attack of the phosphorus at sulfur next to the thiocarbonyl group of xanthane hydride followed by decomposition of the phosphonium intermediate formed to products. The Hammett rho-values for the sulfurisation of substituted triphenyl phosphines and triphenyl phosphites in acetonitrile are approximately -1.0. The entropies of activation are very negative (-114+/-15 J mol-1 K-1) with little dependence on solvent which is consistent with a bimolecular association step leading to the transition state. The negative values of DeltaS(not equal) and rho values indicate that the rate limiting step of the sulfurisation reaction is formation of the phosphonium ion intermediate which has an early transition state with little covalent bond formation. The site of nucleophilic attack has been also confirmed using computational calculations.     

Singlet oxygen photooxygenation of furans : Isolation and reactions of (4+2)-cycloaddition products (unsaturated sec.-ozonides)

Tetraphenylporphin-photosensitized oxygenations of furan (19), 2-methylfuran (26), 2-ethylfuran (39), furfurylalcohol (24), 2-acetylfuran (40), 2-methoxyfuran (42), 2,5-dimethylfuran (30), furfural (25) and 5-methylfurfural (41) in non-polar aprotic solvents yield the corresponding monomeric unsaturated secondary ozonides due to a (4+2)-cycloaddition of singlet oxygen to these furans. With the exception of the ozonide derived from 25, the ozonides were isolated and characterized (¹H- and ¹³C-NMR spectra, etc.). In non-polar aprotic solvents, the ozonides derived from 19, 26 and 39 undergo thermal rearrangements to the corresponding cis-diepoxides and epoxylactones. Ozonide 31, derived from 30, however, dimerizes, only above about 60° is a cis-diepoxide formed from either 31 or its dimer. Rose bengal-photosensitized oxygenations of the furans in alcohols (MeOH, EtOH, i-PrOH) also produce the corresponding ozonides as the primary products of (4+2)-cycloadditions of singlet oxygen to these furans. However, reactions of the alcohols with the ozonides are too fast to allow the ozonides to be isolated. Instead, the same products are obtained as are isolated from reactions carried out by dissolving the ozonides in the alcohols. Depending on the structure of the ozonide, three pathways are available to ozonide/alcohol (ROH) interactions:(1) addition of ROH to yield alkoxy hydroperoxides; one out of several possible isomers is formed in a completely stereoselective and regiospecific reaction; (2) elimination of a bridgehead proton by ROH as a base, as observed with the ozonide derived from 19 to give hydroxy butenolide (78) in yields between 20 and 60%, and (3) ROH-attack on a carbonyl side-chain under elimination of the corresponding alkyl ester, as observed with furfural photooxygenation which yielded hydroxy butenolide (78) in high yields (95%). Interaction of ozonide 31 with tert.-butyl alcohol (t-BuOH) yields quantitatively cis-3-oxo-1-butenylacetate (81) by a Baeyer-Villiger-type rearrangement with vinyl group migration Hydrogenbonding between the alcohol and the peroxy group of the ozonides assist the heterolysis of the C—O bonds in the ozonides; the most stabilized cation develops. Front-attack of ROH on this cation explains the stereoselectivity as well as the regiospecificity of the alkoxy hydroperoxide formation; with a bulky alcohol like t-BuOH, ROH-attack on the cation is sterically hindered thus allowing a rearrangement to occur. 1,3-Dipolar cycloaddition of p-nitrophenyl azide to ozonide 31 proceeds stereoselectively to one of the isomers 87a/87b. Finally, kinetic results of furan photooxygenation in methanol show the following order of furan-reactivity towards singlet oxygen: 30 > 42 > 26 > 19 > 41 > 25, with absolute rate constants ranging from 1.8 × 10⁸ (with 30) to 8.4 × 1O⁴ M^-1P^-1 (with 25).     

Ozone as an oxygen source for alkene ene-reactions

Summary A strategy was developed which uses the adduct of ozone and triphenyl phosphite as a substitute for photochemically generated singlet oxygen in ene reactions of olefins. The resulting allylic hydroperoxide can be conveniently reduced by a second mole of phosphite to yield the corresponding allylic alcohol. The aryl phosphate produced as the by-product can either be recycled by reduction or used itself as a commodity. As an example, the two key steps of the rose oxide synthesis involving singlet oxygen can thus be reduced to a one pot procedure. With respect to the reaction mechanism, additional arguments for the direct reaction of the olefin with the phosphite ozonide were gathered. A simple decomposition of the ozonide to produce singlet oxygen was made rather unlikely.

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Ozon als Sauerstoffquelle für En-Reaktionen von Olefinen

Zusammenfassung Es wurde eine Strategie zum Ersatz von photochemisch erzeugtem Singlett-Sauerstoff durch das Addukt aus Ozon und Triphenylphosphit zum Einsatz in En-Reaktionen von Olefinen entwickelt. Das entstehende allylische Hydroperoxid kann durch ein zweites Molekül Phosphit einfach zum entsprechenden allylischen Alkolhol reduziert werden. Das als Nebenprodukt entstehende Arylphosphat kann entweder durch Reduktion recycliert oder direkt als Handelsware weiterverwendet werden. Auf diese Weise können zum Beispiel die beiden Stufen der Rosenoxidsynthese, an denen Singlett-Sauerstoff beteiligt ist, zu einer Eintopfreaktion vereinfacht werden. Bezüglich des Reaktionsmechanismus wurden zusätzliche Hinweise auf die direkte Reaktion des Phosphitozonids mit dem Olefin gefunden. Eine Zersetzung des Ozonids unter Bildung von Singlettsauerstoff ist nicht wahrscheinlich.

     

Iron,copper and their proteins in substantia nigra of human brain during aging

Liquid-liquid extraction of zirconium(IV) was investigated from dilute hydrochloric acid medium by salicyaldoxime (HA) in dichloromethane. The metal was spiked with ⁹⁵Zr and analyzed by its radioactivity. The effects of different donors, like trioctyl phosphine oxide (TOPO), triphenyl phosphine oxide (TPPO), tributyl phosphine oxide (TBPO), tributyl phosphate (TBP), trioctyl amine (TOA) and Amberlite LA-2 were studied. The adduct formation constants for both binary species (metal-ligand) and ternary species (metal-ligand-donor) were also calculated form the distribution data.One of the authors (S.B.) thanks The University of Burdwan for providing senior research fellowship to her. She also wishes to thank Dr. D. Mukherjee and Dr. S. Bhattacharya, B.U. for their valuable suggestions.     

Possible role of Lewis acid catalysis in the oxidation of alkenes and α,β-unsaturated ketones using bleomycin-zn(ii) and bleomycin-fe(iii)-iodosylbenzene in aqueous methanol

C₆H₅IO in CH₃OH-H₂0 is activated towards electrophilic attack upon various alkenes by Fe(ClO₄).9H₂O, FE(III) bleomycin and ZN(II) bleomycin. The results imply that direct transfer of oxygen from an Fe(V)=0 intermediate is not required in the mechanism of oxygenation by iron-containing species, and that much earlier work is questionable as models for biological oxygenation.     

Kinetics and thermodynamics of limonene ozonolysis

Using density functional methods, the initial reaction steps of limonene ozonolysis have been investigated with a focus on primary ozonide formation and its decomposition to Criegee intermediates and carbonyl compounds. The ozonide formation is highly exothermic, and the decomposition channels have similar free energies of activation, ΔG(?), indicating that there is no primary pathway for ozonide decomposition. Assuming that ozonide formation is the rate limiting step, the theoretical rate coefficient, k = 1.6 × 10(-16) molecule(-1) cm(3) s(-1), evaluated at the CCSD(T)/6-31G(d,p)//BHandHLYP/cc-pvdz level and 298.15 K for d-limonene is in good agreement with the experimental value, k(exp) = 3.3 × 10(-16) molecule(-1) cm(3) s(-1). The theoretical Arrhenius expression is also in good agreement with experimental results.     

The coordination of perrhenate and pertechnetate to thorium(IV) in the presence of phosphine oxide or phosphate ligands

A series of thorium(IV) perrhenato- and pertechnetato-complexes with P[double bond, length as m-dash]O donor ligands have been prepared and characterised both in the solid state and in solution. Isostructural complexes of general formula [Th(MO(4))(4)(L)(4)], where M = Re or Tc and L = triethylphosphate (TEP) (2 and 7), tri-iso-butylphosphate (TiBP) (3 and 8) and tri-n-butylphosphine oxide (TBPO) (4 and 9) have been prepared from the novel starting materials [Th(ReO(4))(4)] x 4H(2)O (1) and [Th(TcO(4))(4)] x 4H(2)O (6). The reaction of or with triphenylphosphine oxide (TPPO) in MeOH has also led to the synthesis of [Th(MO(4))(3)(TPPO)(3)(OCH(3))(HOCH(3))] (M = Re (5) or Tc (10)). While the structural characterisation of 4 and 9 has been previously described, we report for the first time the structural characterisation of 2 and 5, with a partial structural refinement of 3. Vibrational spectroscopic analysis confirms that the Tc complexes not characterised by single crystal X-ray diffraction are indeed isostructural with the perrhenate complexes with the same P[double bond, length as m-dash]O donor ligand. In all cases, monodentate coordination of the Group 7 tetraoxo anion is observed. (31)P NMR spectroscopy indicates that in all the phosphine oxide-based complexes there is one dominant solution species. For the phosphate based systems, the presence of pertechnetate appears to inhibit P[double bond, length as m-dash]O donor ligand complexation in solution, whereas a significant proportion of each phosphate remains coordinated to Th(IV) when perrhenate is present as the counter ligand. These results give some indication as to the mechanism of pertechnetate co-extraction with tetravalent cations in the presence of tri-n-butyl phosphate in the Plutonium and Uranium Recovery by Extraction (PUREX) process.     

Überraschende Ergebnisse bei der Nachprüfung der Bildung und Zersetzung von Tripten‐ozonid

Surprising Results during the Re‐investigation of the Formation and Decomposition of Triptene Ozonide . Revision of the ozonolysis of triptene (=2,3,3‐trimethylbut‐1‐ene; 1 ) revealed that molecular oxygen of an applied ozone/oxygen gas mixture participates as well in the cleavage of the C=C bond as in the ozonide formation. Ozone‐to‐olefin stoichiometry varies in the range of 0.64 – 0.95 : 1 in terms of complete olefin consumption, depending on solvents, on reaction temperature, and on reaction conditions. Thermal decomposition of distilled monomeric triptene ozonide ( 2 ) does not lead to 3,6‐di(tert‐butyl)‐3,6‐dimethyl‐1,2,4,5‐tetroxane ( 5 ), which is formed by formaldehyde extrusion from an unstable oligomeric (probably dimeric) triptene ozonide 2 ′. Acid‐catalyzed decomposition of 2 exclusively yields pinacolone ( 7 ) and formic acid ( 9 ).     

The synthesis, structural, and spectroscopic characterization of uranium(IV) perrhenate complexes

We report the synthesis, structural, and spectroscopic characterization of a series of uranium(IV)-perrhenato complexes. Three isostructural complexes with general formula [U(ReO4)4(L)4] (where L = tri-n-butylphosphine oxide/TBPO (2), triethyl phosphate/TEP (3), or tri-iso-butyl phosphate/TiBP (4)), have been synthesized, both through the photoreduction of ethanolic {UO2}2+ solutions and also via a novel U(IV) starting material, U(ReO4)4.5H2O (1). Compound 1 has also been used in the preparation of [U(ReO4)4(TPPO)3(CH3CN)].2CH3CN (5) and [U(ReO4)(DPPMO2)3(OH)][ReO4]2.2CH3CN (6), where TPPO represents triphenylphosphine oxide and DPPMO2 represents bis(diphenylphosphino)methane dioxide. All six complexes have been spectroscopically characterized using NMR, UV-vis-NIR, and IR techniques, with 2, 3, 5, and 6 also fully structurally characterized. The U atoms in compounds 2-6 all exhibit eight-coordinate geometry with up to four perrhenate groups in addition to three (DPPMO2 and TPPO) or four (TEP, TiBP, TBPO) coordinated organic ligands. In the case of compounds 5 and 6, the coordination of eight ligands to the U(IV) center is completed by the binding of a solvent molecule (CH3CN) and OH-, respectively. Solid-state physical analysis (elemental and thermogravimetric) and infrared spectroscopy are in agreement with the structural studies. The crystallographic data suggest that the strength of the U(IV)-O-donor ligand bonds decreases across the series R3PO > [ReO4]- > (RO)3PO. Solution-state IR and 31P NMR spectroscopy appear to be in agreement with these solid-state results.