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https://hdl.handle.net/2440/73927
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Type: | Journal article |
Title: | Oxidative dimerization of aryldiynyl-ruthenium complexes |
Author: | Bruce, M. Costuas, K. Gendron, F. Halet, J. Jevric, M. Skelton, B. |
Citation: | Organometallics, 2012; 31(18):6555-6566 |
Publisher: | Amer Chemical Soc |
Issue Date: | 2012 |
ISSN: | 0276-7333 1520-6041 |
Statement of Responsibility: | Michael I. Bruce, Karine Costuas, Frédéric Gendron, Jean-François Halet, Martyn Jevric, and Brian W. Skelton |
Abstract: | Chemical oxidation of Ru(C≡CC≡CR)(dppe)Cp with [FeCp 2]PF 6 affords the binuclear cations [{Ru(dppe)Cp} 2C 8R 2] 2+(PF 6-) 2 (R = Ph, 7 2+(PF 6-) 2; R = Fc, 8 2+(PF 6-) 2) by radical coupling at electron-rich sites involving the inner and outer C≡C triple bonds, to give cyclobutenediylidene derivatives. In each case, mixtures of symmetrical and asymmetrical isomers were obtained (2:1 for 7 2+(PF 6-) 2, 1:1 for 8 2+(PF 6-) 2), shown by single-crystal X-ray diffraction structure determinations of 7 2+-asym(PF 6-) 2 and 8 2+-sym(AsF 6-) 2. 8 2+-sym consists of a central C 4 ring with two =C=C=Ru(dppe)Cp groups in the 1,2-positions and two Fc substituents in the 3,4-positions, whereas for 7 2+-asym the substituent =Ru(dppe)Cp is in the 1-position, =C=C=Ru(dppe)Cp is in the 2-position, Ph is in the 3-position, and -C≡CPh is in the 4-position. DFT calculations reveal that the precursor cationic diynyl complexes show important electron density on C β and C δ, suggesting that radical coupling (C δ + C δ) or (C β + C δ) affords the sym and asym isomers, respectively. © 2012 American Chemical Society. |
Rights: | Copyright © 2012 American Chemical Society |
DOI: | 10.1021/om3005146 |
Published version: | http://dx.doi.org/10.1021/om3005146 |
Appears in Collections: | Aurora harvest 4 Chemistry publications |
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