Uranium(III)-mediated C-C-coupling of terminal alkynes: Formation of dinuclear uranium(IV) vinyl complexes
Kosog B, Kefalidis CE, Heinemann FW, Maron L, Meyer K (2012)
Publication Type: Journal article, Original article
Publication year: 2012
Journal
Original Authors: Kosog B., Kefalidis C.E., Heinemann F.W., Maron L., Meyer K.
Publisher: American Chemical Society
Book Volume: 134
Pages Range: 12792-12797
Journal Issue: 30
DOI: 10.1021/ja3047393
Abstract
The previously reported uranium(III) complex [(( ArO) N)U (DME)] (1; Ad = adamantane, DME = 1,2-dimethoxyethane) reacts with the terminal bis-alkynes 1,7-octadiyne or 1,6-heptadiyne in C-C-coupling reactions to form the uranium(IV) vinyl complexes [{(( ArO) N)U } (μ- η :η -1,2-(CH) -cyclohexane)] (2) and [{(( ArO) N)U } (μ- η :η -1,2-(CH) -cyclopentane)] (3). With the monoalkynes 1-hexyne or 4- butyl-phenylacetylene, the complexes [{(( ArO) N)U } (μ- η (C1):η (C4)-2- Bu-1,3-octadiene)] (4) and [{(( ArO) N)U } (μ- η (C4):η (C1)-1,3-di-(p- Bu-phenyl) butadiene))] (5), are formed. These are the first four examples of uranium vinyl complexes that are reported and crystallographically characterized. In addition, detailed DFT calculations are presented to establish a possible mechanism for their formation and explain the differences found for the coordination of the hydrocarbon fragments. In contrast to a previously proposed monometallic pathway for catalytic hydroamination of alkynes and alkyne dimerization involving a uranium vinyl intermediate at uranium(III) complexes, the calculations clearly support a bimetallic mechanism, since its transition states are energetically the most favored. © 2012 American Chemical Society.
Authors with CRIS profile
Boris Kosog
Lehrstuhl für Anorganische und Allgemeine Chemie
Frank Wilhelm Heinemann
Lehrstuhl für Anorganische und Allgemeine Chemie
Karsten Meyer
Lehrstuhl für Anorganische und Allgemeine Chemie
Involved external institutions
France (FR)How to cite
APA:
Kosog, B., Kefalidis, C.E., Heinemann, F.W., Maron, L., & Meyer, K. (2012). Uranium(III)-mediated C-C-coupling of terminal alkynes: Formation of dinuclear uranium(IV) vinyl complexes. Journal of the American Chemical Society, 134(30), 12792-12797. https://doi.org/10.1021/ja3047393
MLA:
Kosog, Boris, et al. "Uranium(III)-mediated C-C-coupling of terminal alkynes: Formation of dinuclear uranium(IV) vinyl complexes." Journal of the American Chemical Society 134.30 (2012): 12792-12797.
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