Comparison of the Reactivity of 2-Li-C6H4CH2NMe2 with MCl4 (M=Th, U): Isolation of a Thorium Aryl Complex or a Uranium Benzyne Complex

Comparison of the Reactivity of 2-Li-C6H4CH2NMe2 with MCl4 (M=Th, U): Isolation of a Thorium Aryl Complex or a Uranium Benzyne Complex

Why do U react like that? Reaction of 2‐Li‐C6H4CH2NMe2 with [MCl4(DME)n] (M=Th, n=2; M=U, n=0) results in the formation of a thorium aryl complex, [Th(2‐C6H4CH2NMe2)4] or a uranium benzyne complex, [Li][U(2,3‐C6H3CH2NMe2)(2‐C6H4CH2NMe2)3]. A DFT analysis suggests that the formation of a benzyne comp...

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Veröffentlicht in:Angewandte Chemie International Edition 2013-09, Vol.52 (40), p.10589-10592
Hauptverfasser: Seaman, Lani A., Pedrick, Elizabeth A., Tsuchiya, Takashi, Wu, Guang, Jakubikova, Elena, Hayton, Trevor W.
Format: Artikel
Sprache:eng
Schlagworte:
aryl
benzyne
bonding analysis
thorium
uranium
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Zusammenfassung:Why do U react like that? Reaction of 2‐Li‐C6H4CH2NMe2 with [MCl4(DME)n] (M=Th, n=2; M=U, n=0) results in the formation of a thorium aryl complex, [Th(2‐C6H4CH2NMe2)4] or a uranium benzyne complex, [Li][U(2,3‐C6H3CH2NMe2)(2‐C6H4CH2NMe2)3]. A DFT analysis suggests that the formation of a benzyne complex with U but not with Th is a kinetic and not thermodynamic effect.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201303992