Convenient syntheses of uranyl(VI) cis-dihalide complexes as anhydrous starting materials

Duval, Paul; Kannan, S.; Barnes, Charles L.

doi:10.1016/j.inoche.2006.01.023

Cited by 14 publications

(18 citation statements)

References 24 publications

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“…The U(1)–N(2) (U-N pyridine ) and U(1)–O(3) (U-O THF ) bond distances for ( Mes PDP Ph )UO 2 (THF) are 2.535(2) and 2.3917(19) Å, respectively. For comparison, the U–N pyridine bond distance is shorter than that of the pyridine-2,6-dicarboxamide complex uranyl complex UO 2 Cl 2 L 97 (L = N , N , N ′, N ′-tetraalkylpyridine-2,6-dicarboxamide) possessing (U–N pyridine 2.634(2) Å); however, the U–O THF distance is in good agreement with the average U–O THF bond distance found in [UO 2 Cl 2 (THF) 2 ] 2 (2.40(3) Å). 98 Completing the primary coordination sphere, the ( Mes PDP Ph )UO 2 (THF) U–N pyrrole contacts, U(1)–N(1) and U(1)–N(3), were determined to be 2.354(2) and 2.356(2) Å, which are shorter than in dipyriamethyrin and dipyrrinate analogues.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Pyridine Dipyrrolide Uranyl Complexes

et al. 2022

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The first actinide complexes of the pyridine dipyrrolide (PDP) ligand class, ( Mes PDP Ph )UO 2 (THF) and ( Cl2Ph PDP Ph )UO 2 (THF), are reported as the U VI uranyl adducts of the bulky aryl substituted pincers ( Mes PDP Ph ) 2– and ( Cl2Ph PDP Ph ) 2– (derived from 2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1 H -pyrrol-2-yl)pyridine (H 2 Mes PDP Ph , Mes = 2,4,6-trimethylphenyl), and 2,6-bis(5-(2,6-dichlorophenyl)-3-phenyl-1 H -pyrrol-2-yl)pyridine (H 2 Cl2Ph PDP Ph , Cl 2 Ph = 2,6-dichlorophenyl), respectively). Following the in situ deprotonation of the proligand with lithium hexamethyldisilazide to generate the corresponding dilithium salts (e.g., Li 2 Ar PDP Ph , Ar = Mes of Cl 2 Ph), salt metathesis with [UO 2 Cl 2 (THF) 2 ] 2 afforded both compounds in moderate yields. The characterization of each species has been undertaken by a combination of solid- and solution-state methods, including combustion analysis, infrared, electronic absorption, and NMR spectroscopies. In both complexes, single-crystal X-ray diffraction has revealed a distorted octahedral geometry in the solid state, enforced by the bite angle of the rigid meridional ( Ar PDP Ph ) 2– pincer ligand. The electrochemical analysis of both compounds by cyclic voltammetry in tetrahydrofuran (THF) reveals rich redox profiles, including events assigned as U VI /U V redox couples. A time-dependent density functional theory study has been performed on ( Mes PDP Ph )UO 2 (THF) and provides insight into the nature of the transitions that comprise its electronic absorption spectrum.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Pyridine Dipyrrolide Uranyl Complexes

et al. 2022

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“…For UO 2 2+ , the coordination structures of its complexes with a series of neutral diamide ligands in the solid state have been determined using single crystal X-ray diffraction. − The diglycolamides, , dipicolinates, and the corresponding diamides − act as tridentate chelating ligands in the uranyl complexes while glutaramides , and thiodiglycolamides were found to bind the uranium center in bidentate fashions. Compared with the rich studies on the solid state structures of the uranyl–diamide complexes, limited information is available on the structures of these complexes in solution and gas phase.…”

Section: Introductionmentioning

confidence: 99%

Coordination Structures of the Uranyl(VI)–Diamide Complexes: A Combined Mass Spectrometric, EXAFS Spectroscopic, and Theoretical Study

Chen

Gong

2019

Inorg. Chem.

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The coordination structures of a series of uranyl–diamide complexes, namely UO2(TMGA)2 2+, UO2(TMTDA)2 2+, and UO2(TMPDA)2 2+ (TMGA: N,N,N′,N′-tetramethylglutaramide; TMTDA: N,N,N′,N′-tetramethyl-3-thiodiglycolamide; TMPDA: N,N,N′,N′-tetramethylpyridine-2,6-dicarboxamide), in the gas phase and solution were studied by electrospray ionization (ESI) mass spectrometry, density functional theory (DFT) calculations, and extended X-ray absorption fine structure (EXAFS) spectroscopy. ESI of UO2Cl2–TMGA, UO2Cl2–TMTDA, and UO2Cl2–TMPDA solutions produced UO2(TMGA)2 2+, UO2(TMTDA)2 2+, and UO2(TMPDA)2 2+ as the major complexes in the gas phase. The gas-phase fragmentation patterns of these three complexes upon collision-induced dissociation (CID) are quite similar, and the products arising from (CH3)2N–COcarbonyl, CH2–COcarbonyl, Cpyridine–COcarbonyl, and CH2–CH2/S bond cleavages were identified, which agree with the degradation patterns of diamides upon γ irradiation in solution. DFT calculations revealed similar bidentate coordination modes of TMGA and TMTDA in the UO2(TMGA)2 2+ and UO2(TMTDA)2 2+ complexes in the gas phase. For UO2(TMPDA)2 2+, UO2 2+ is coordinated by two Ocarbonyl and one Npyridine from each TMPDA, which acts as a tridentate ligand. The results from EXAFS analysis indicate that the coordination structures of UO2(TMGA)2 2+, UO2(TMTDA)2 2+, and UO2(TMPDA)2 2+ in solution are similar to those in the gas phase.

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“…The preparation of the air and moisture sensitive complex [UO 2 Cl 2 (thf) 2 ] 2 [1] facilitated a significant increase in nonaqueous uranyl chemistry, and is nowadays a widely used precursor to synthesise new uranyl(VI) species such as [Na(thf) 2 ][UO 2 {N(SiMe 3 ) 2 } 3 ] [2], with a coordination number of three in the equatorial plane and the first examples of uranyl-carbon bonds in [UO 2 Cl 2 (IMes) 2 ] (IMes = 1,3 dimesitylimidazol-2-ylidene or 1,3, dimesityl-4,5 dichloroimidazol-2-ylidene) [3]. In addition [UO 2 (OTf) 2 ] has also been used in the preparation of uranyl complexes under inert atmosphere [4] ubility (in comparison with [UO 2 Cl 2 (thf) 2 ] 2 ), which could be used as new starting materials to enter air and moisture sensitive chemistry of the uranyl cation [5,6]. Removing moisture eliminates the possibility of hydrolysis and hence competition with strong oxo and hydroxy donor ligands.…”

Section: Introductionmentioning

confidence: 99%