Insertion of carbonyl compounds into actinide—carbon σ bonds: Reactivity of [(Me3Si)2)2N]2SiMe3

Dormond, A.; Bouadili, A. El; Aaliti, A.; Moı̈se, Claude

doi:10.1016/0022-328x(85)80111-x

Cited by 47 publications

(46 citation statements)

References 16 publications

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“…2 As an added complication, it was observed that in solution UQCHPPh 3 (NR 2 ) 3 exists in equilibrium with free Ph 3 PQCH 2 and the U(IV) metallacycle U(CH 2 SiMe 2 NR)(NR 2 ) 2 (Scheme 3). 45,46 This equilibrium was found to be highly dependent upon temperature, which actually proved to be quite beneficial, as it allowed us to determine the thermodynamic parameters of the equilibrium. A van't Hoff plot revealed that the forward reaction is endothermic (DH = 11 kcal mol À1 ) but highly entropically favoured (DS = 31 eu).…”

Section: Complexes Containing the Carbene Ligandmentioning

confidence: 99%

Recent developments in actinide–ligand multiple bonding

2013

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In the last few years, considerable progress has been made in the synthesis and characterization of complexes containing actinide-ligand multiple bonds, especially in regards to isolation of terminal oxo, nitrido and carbene-containing complexes. This review summarizes the synthesis, structure, and reactivity of these complexes, from 2010 until present. These complexes are of interest for a variety of reasons, including their potential use in novel catalytic transformations and their ability to engage the 5f orbitals in metal-ligand bonding. Of particular note are the recent syntheses of the first isolable complex containing the nitride-substituted uranyl ion, [NUO](+), and the first report of an isolable terminal uranium nitride. Considerable progress has also been made toward the syntheses of actinide carbenes and thorium complexes containing metal-ligand multiple bonds.

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Section: Complexes Containing the Carbene Ligandmentioning

confidence: 99%

Recent developments in actinide–ligand multiple bonding

2013

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“…[27] The subsequent nucleophilic additiono ft he methylene unit to the adjacent carbonyl group leads to the product of CÀCc oupling which upon coordinationo ft he cerium ion by an additional Ph 2 CO molecule gives the final product 6.T he same reactivity between the metallacycle of type (6c)a nd carbonyls was described for the relatedUand Th metallacycles. [28] Notably,c omplex 1 does not show the formation of HN(SiMe 3 ) 2 when heatedi nabenzene solution at 120 8Cf or 4days. This observation indicates that the coordination of Ph 2 C=Oisakeystep toward the formation of ametallacycle.…”

Section: Reactivity Studiesmentioning

confidence: 99%

Structure, Electronics and Reactivity of Ce(PNP) Complexes

Zabula

Qiao

Kosanovich

et al. 2017

Chemistry A European J

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Synthetic methods for the coordination of the monoanionic bis[2-(diisopropylphosphino)-4-methylphenyl]amido (PNP) ligand framework to the cerium(III) cation have been developed and applied for the isolation of a series of {(PNP)Ce} and {(PNP) Ce} type complexes. The structures of the complexes were studied by X-ray diffraction and multinuclear NMR spectroscopy. We found that the cerium(III) ion can induce the elimination of one of the iPr groups at phosphorus to yield a new dianionic PNP tridentate framework (PNP ) featuring a phosphido-donor functionality, which is bound to the cerium ion with the shortest known Ce-P bond of 2.7884(14) Å for molecular compounds. The reaction of the complex [(PNP)Ce{N(SiMe ) } ] (1) with Ph CO gave the Ce-bound product of C-C coupling, N(SiMe )SiMe CH -CPh O , through the C-H bond activation of a SiMe group. P NMR spectroscopy was used to estimate the presence of a vacant coordination position at the cerium ion in the Ce -PNP complexes by the examination of the δ( P) shift recorded both in non-polar (C D ) and polar ([D ]THF) solvents. Moreover, P NMR spectroscopy was also found to be a useful tool for the estimation of the Ce-P bond distances in {(PNP)Ce } and {(PNP) Ce } systems. Electrochemical and computational studies for 1 and its lanthanum analogue containing a redox-innocent metal center revealed the stabilization of the Ce oxidation state by the PNP ligand.

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“…PhOH, 2,6-dimethylphenol (2,6-Me 2 PhOH), 2,4-di- tert -butylphenol, Ph 2 CHOH, 1-adamantanol, and 1,3-di- p -tolylcarbodiimide (Sigma-Aldrich) were dried for 12 h on a high vacuum line (10 –5 Torr) and stored in a glovebox prior to use. The actinide metallacycles were prepared according to previous reports . Deuterated 2,4-di- tert -butylphenol (2,4- t Bu 2 PhOD) was prepared using a similar method according to published procedures .…”

Section: Methodsmentioning

confidence: 99%

“…The actinide metallacycles were prepared according to previous reports. 73 Deuterated 2,4-di-tert-butylphenol (2,4-t Bu 2 PhOD) was prepared using a similar method according to published procedures. 74 1,3-Di-(2,4,6-trimethylphenyl)carbodiimide, 75 1,3-di-p-chlorophenylcarbodiimide, 76 and 1,3-di-p-methoxylphenylcarbodiimide, 76 were prepared according to previous reports.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Catalytic Addition of Alcohols to Carbodiimides Mediated by Benzimidazolin-2-iminato Actinide Complexes

et al. 2017

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The synthesis of methyl and methoxy substituted benzimidazolin-2-iminato actinide (IV) complexes (1−4), [(Bim 2-MeOPh/Me N)AnN″ 3 ] and [(Bim 5-Me Dipp/Me N)-AnN″ 3 ] (An = U, Th; N″ = N(SiMe 3 ) 2 ), was performed by the protonolysis of the actinide metallacycles with the respective neutral benzimidazolin-2-imine ligand precursors. Full characterization, including X-ray diffraction studies for all the complexes, is reported. Despite the high oxophilicity of the actinide metal centers, these complexes displayed extremely high activities in the catalytic addition of aliphatic and aromatic alcohols to carbodiimides, under very mild conditions, providing a facile and highly efficient strategy for the construction of carbon−oxygen bonds. Various kinds of diols and triols can also be used in this intermolecular insertion, representing a large substrate scope for the application of these organoactinide precatalysts.

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Insertion of carbonyl compounds into actinide—carbon σ bonds: Reactivity of [(Me3Si)2)2N]2SiMe3

Cited by 47 publications

References 16 publications

Recent developments in actinide–ligand multiple bonding

Recent developments in actinide–ligand multiple bonding

Structure, Electronics and Reactivity of Ce(PNP) Complexes

Catalytic Addition of Alcohols to Carbodiimides Mediated by Benzimidazolin-2-iminato Actinide Complexes

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