Solid-state studies of the Horner–Wittig reagent [{{Ph2P(O)}2CHLi·(THF)}2·THF] and its mixed-anion intermediate [{{Ph2P(O)}2CHLi}4·{Ph2P(O)2Li} 2·8C6H6] formed by reaction with dioxygen

Nassar, Roger; Noll, Bruce C.; Henderson, Kenneth W.

doi:10.1016/j.poly.2004.08.017

Cited by 13 publications

(5 citation statements)

References 43 publications

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“…The β-diphosphine oxide anion ligand has precedent in the chemical literature. For instance, it is formed by deprotonation of DPPMO 2 by either n -BuLi or AlMe 3 . , Furthermore, the nitrogen analogue of the β-diphosphine oxide anion, [CH(Ph 2 PNSiMe 3 )] - , has been ligated to uranyl . This ligand coordinates to the uranyl fragment in a tridentate fashion, through both nitrogen donors and the bridging methine carbon.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis, Characterization, and Reactivity of a Uranyl β-Diketiminate Complex

Hayton

2008

J. Am. Chem. Soc.

101

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Addition of 1 equiv of Li(Ar2nacnac) (Ar2nacnac = (2,6-(i)Pr2C6H3)NC(Me)CHC(Me)N(2,6-(i)Pr2C6H3)) to an Et2O suspension of UO2Cl2(THF)3 generates the uranyl dimer [UO2(Ar2nacnac)Cl]2 (1) in good yield. A second species can be isolated in low yield from the reaction mixtures of 1, namely [Li(OEt2)2][UO2(Ar2nacnac)Cl2] (2). The structures of both 1 and 2 have been confirmed by X-ray crystallography. Complex 1 reacts with Ph3PO to generate UO2(Ar2nacnac)Cl(Ph3PO) (3). In addition, 1 reacts with AgOTf and either 1 equiv of DPPMO2 or 2 equiv of Ph2MePO to provide [UO2(Ar2nacnac)(DPPMO2)][OTf] (4) and [UO2(Ar2nacnac)(Ph2MePO)2][OTf] (5), respectively. Both 4 and 5 have been fully characterized, including analysis by X-ray crystallography and cyclic voltammetry. Reduction of 4 with Cp2Co provides UO2(Ar2nacnac)(CH{Ph2PO}2) (6), a uranyl(VI) complex that is generated by the formal loss of H* from the DPPMO2 ligand. Labeling studies have been performed in an attempt to elucidate the mechanism of hydrogen loss. In contrast, reduction of 5 with Cp2Co provides UO2(Ar2nacnac)(Ph2MePO)2 (7), a rare example of a uranyl(V) complex. As expected, the solid-state molecular structure of 7 reveals slightly longer U-O(oxo) bond lengths relative to 5. Furthermore, complex 7 can be converted back into 5 by oxidation with AgOTf in toluene.

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Section: Resultsmentioning

confidence: 99%

“…39(2) Å, Li1-Cl2 ) 2. 35(2) Å) and two molecules of diethyl ether (Li1-O3 ) 1.94(2) Å, Li1-O4 ) 1.95(2) Å), resulting in a tetrahedral geometry. The bond lengths and angles of the lithium cation are as expected.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Characterization, and Reactivity of a Uranyl β-Diketiminate Complex

Hayton

2008

J. Am. Chem. Soc.

101

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“…Like enolates, sulfoxides, and sulfones, lithiated phosphine oxides, phosphonates, and phosphonamides are often O-lithiated in the solid state. A solid-state tetramer in which Li–O links form the central cube, with each lithium chelated by the carbanion carbon, has been reported .…”

Section: Structures Of Organolithium Reagentsmentioning

confidence: 99%

Role of Organolithium Aggregates and Mixed Aggregates in Organolithium Mechanisms

2013

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“…During the course of these investigations we have synthesized and structurally characterized the a,a -stabilized monocarbanions of several systems including cyanophosphonates, 12 (organosulfonyl)acetonitriles, 13 b-diphosphonates, 14 and b-diphosphine oxides. 15 These monocarbanions display unexpected aggregation behaviors compared to their singly a-stabilized analogues, and we have begun to establish new structural patterns within this area. In an extension to this work we now report the synthesis and characterization of the monocarbanions and the geminal dianions of bis(phenylsulfonyl)methane using lithium, sodium and potassium as the countercations.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of mono- and geminal dimetalated carbanions of bis(phenylsulfonyl)methane using alkali metal bases and structural comparisons with lithiated bis(phenylsulfonyl)imides

et al. 2005

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The alpha,alpha'-stabilized carbanion complexes [(PhSO2)2CHLi.THF]1, [(PhSO2)2CHNa.THF]2 and [(PhSO2)2CHK]3 were prepared by the direct deprotonation of bis(phenylsulfonyl)methane I in THF with one molar equivalent of MeLi, BuNa and BnK respectively. The geminal dianionic complexes [(PhSO2)2CLi2.THF]4, [(PhSO2)2CNa2.0.55THF]5 and [(PhSO2)2CK2]6 were similarly prepared by the reaction of I with two molar equivalents of MeLi, BuNa and BnK respectively in THF. NMR and MS solution studies of 1-3 are consistent with the formation of charge-separated species in DMSO media. Solutions studies of 4-6, in conjunction with trapping experiments, indicate that the dianions deprotonate DMSO and regenerate the monoanions 1-3. Crystallographic analysis of 1 revealed a 1D chain polymer in which the metal centers are chelated by the bis(sulfonyl) ligands and connect to neighboring units through Li-O(S) interactions. An unexpected feature of 1 is that the polymeric chains are homochiral, since the chelating ligands of the backbone adopt the same relative configuration. Also, the phenyl substituents of each chelate in 1 are oriented in a cisoid manner. The sodium derivative 2 adopts a related solid-state structure, where enantiomeric pairs of chains combine to give a 1D ribbon motif. The lithium bis(phenylsulfonyl)imides [(PhSO2)2NLi.THF]9 and [(PhSO2)2NLi.Pyr2]10 were also prepared and structurally characterized. In the solid state 9 has a similar connectivity to that found for 1 but with heterochiral chains. In comparison, the more highly solvated complex 10 forms a 1D polymeric arrangement without chelation of the ligands and with the phenyl substituents oriented in a transoid fashion.

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Solid-state studies of the Horner–Wittig reagent [{{Ph2P(O)}2CHLi·(THF)}2·THF] and its mixed-anion intermediate [{{Ph2P(O)}2CHLi}4·{Ph2P(O)2Li} 2·8C6H6] formed by reaction with dioxygen

Cited by 13 publications

References 43 publications

Synthesis, Characterization, and Reactivity of a Uranyl β-Diketiminate Complex

Synthesis, Characterization, and Reactivity of a Uranyl β-Diketiminate Complex

Role of Organolithium Aggregates and Mixed Aggregates in Organolithium Mechanisms

Synthesis of mono- and geminal dimetalated carbanions of bis(phenylsulfonyl)methane using alkali metal bases and structural comparisons with lithiated bis(phenylsulfonyl)imides

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