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• W2055291257 abstract "Laser ablation with prompt reaction and detection was applied to study gas-phase reactions of actinide ions, An+ and AnO+ [An = Th, U, Pu, Np, Am], with nitriles and butylamine; Tb and Tm were included for comparison. Particular emphasis was on Np and Am as this is the region of the An series where a transition to Ln-like character is manifested. A goal was to assess the role of the coordinating N: site on actinide ion−molecule interactions. The results for the nitriles were generally reminiscent of those for reactions with alkenes and the inert character of Pu+ and Am+ with regard to dehydrogenation, despite adduct formation, indicated that C−H activation requires two non-5f electrons to produce a C−An+−H complex. With the butyronitriles and valeronitrile, Am+ produced AmC2H4+, possibly via an “ion/dipole” interaction. Most MO+ exhibited only adduct formation with the nitriles although ThO+ was distinctively reactive, consistent with a description of Th as a quasi-d-block element. Both Np+ and Tb+ were substantially effective at dehydrogenating butylamine and Am+ exhibited a lesser degree of reactivity. Reactions of the MO+, TbO+, NpO+, and AmO+ with butylamine revealed a dramatic effect of oxo-ligation: AmO+ was at least as reactive as TbO+ and NpO+. It is postulated that the MO+ reactions proceeded via a multicentered intermediate without insertion into a C−H bond. Bis-complexes were produced with nitriles and butylamine, attesting to strong complexation with the :N functionality. An ancillary discovery was Am2+−An dimers/clusters should elucidate the nature of actinide intermetallic bonding, including the role of 5f electrons." @default.
• W2055291257 created "2016-06-24" @default.
• W2055291257 creator A5013277909 @default.
• W2055291257 date "1998-12-10" @default.
• W2055291257 modified "2023-10-16" @default.
• W2055291257 title "Actinide Gas-Phase Chemistry: Reactions of An⁺ and AnO⁺ [An = Th, U, Np, Pu, Am] with Nitriles and Butylamine" @default.
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• W2055291257 doi "https://doi.org/10.1021/ic980908e" @default.
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