Kosog B, Kefalidis CE, Heinemann FW, Maron L, Meyer K (2012)
Publication Type: Journal article, Original article
Publication year: 2012
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
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.
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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