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Syntheses and Structures of Buta-1,3-Diynyl Complexes from ‘On Complex’ Cross-Coupling Reactions

Oerthel, M.-C.; Yufit, D.S.; Fox, M.A.; Bryce, M.R.; Low, P.J.

Syntheses and Structures of Buta-1,3-Diynyl Complexes from ‘On Complex’ Cross-Coupling Reactions Thumbnail


Authors

M.-C. Oerthel

D.S. Yufit

P.J. Low



Abstract

The Pd(PPh3)4/CuI-cocatalyzed reaction of Ru(C≡CC≡CH)(PPh3)2Cp (2) with aryl iodides, Ar–I (3, Ar = C6H4CN-4 (a); C6H4Me-4 (b); C6H4OMe-4 (c); 2,3-dihydrobenzo[b]thiophene (d); C5H4N (e)) proceeds smoothly in diisopropylamine and under an inert atmosphere to give the substituted buta-1,3-diynyl complexes Ru(C≡CC≡CAr)(PPh3)2Cp (4a–e) in moderate to good yield. The procedure allows the rapid preparation of a range of metal complexes of arylbuta-1,3-diynyl ligands without necessitating the prior synthesis of the individual buta-1,3-diynes as ligand precursors. Similar reaction of 2 with half an equivalent of 1,4-diiodobenzene affords the bimetallic derivative {Ru(PPh3)2Cp}2(μ-C≡CC≡C-1,4-C6H4–C≡CC≡C) (5). In the presence of atmospheric oxygen, homocoupling of the diynyl reagent 2 takes place to provide the octa-1,3,5,7-tetrayndiyl complex {Ru(PPh3)2Cp}2(μ-C≡CC≡CC≡CC≡C) (6). Crystallographically determined molecular structures are reported for five complexes (4a, 4b, 4d, 5, and 6). Quantum chemical calculations indicate that the HOMOs are mainly located on the C4–C6H4–C4 and C8 bridges for 5 and 6, respectively, while spectroelectrochemical (UV–vis–NIR and IR) studies on 6 establish that oxidation takes place at the C8 bridge, likely followed by cyclodimerization reactions of the bridging ligand.

Citation

Oerthel, M., Yufit, D., Fox, M., Bryce, M., & Low, P. (2015). Syntheses and Structures of Buta-1,3-Diynyl Complexes from ‘On Complex’ Cross-Coupling Reactions. Organometallics, 34(11), 2395-2405. https://doi.org/10.1021/om501186c

Journal Article Type Article
Publication Date Jun 8, 2015
Deposit Date Mar 3, 2015
Publicly Available Date Mar 12, 2015
Journal Organometallics
Print ISSN 0276-7333
Electronic ISSN 1520-6041
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 34
Issue 11
Pages 2395-2405
DOI https://doi.org/10.1021/om501186c
Public URL https://durham-repository.worktribe.com/output/1413981

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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © 2015 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/om501186c.






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