1996
DOI: 10.1021/om9601110
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Abstract: The ruthenium hydride complexes C 5 Me 5 Ru(L)H 3 (L ) PPh 3 (1a), PCy 3 (1b), PMe 3 (1c)) were found to catalyze the dimerization reaction of terminal alkynes RCtCH (R ) Ph, t-Bu, SiMe 3 , CH 2 Ph, C 4 H 9 ) to produce cis-and trans-1,4-disubstituted enynes RCHdCHCtCR and 1,3-disubstituted enynes CH 2 dC(R)CtCR. The selective product formation was effected by modulating both the catalyst environment and the alkyne substrates. A rare form of dimer, cumulene PhCH 2 CHdCdCdCHCH 2 Ph (5d), was cleanly obtained fr… Show more

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Cited by 142 publications
(76 citation statements)
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“…The major products in the dimerization reaction are E-and Z-1,3-diphenyl-1-buten-3-yne which are readily distinguished by comparison of their 1 H NMR spectra with literature data. The Z-isomer has a pair of doublets at 5.79 and 6.41 ppm (J cis ¼ 11.7 Hz) while the E-isomer has a much larger coupling constant (J trans ¼ 16.2 Hz) for its two doublets at 6.30 and 7.04 ppm [11]. The ratio of the Z:E isomers is found to be 2:1 from integration of the spectra recorded after 24 h of reaction.…”
Section: Resultsmentioning
confidence: 87%
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“…The major products in the dimerization reaction are E-and Z-1,3-diphenyl-1-buten-3-yne which are readily distinguished by comparison of their 1 H NMR spectra with literature data. The Z-isomer has a pair of doublets at 5.79 and 6.41 ppm (J cis ¼ 11.7 Hz) while the E-isomer has a much larger coupling constant (J trans ¼ 16.2 Hz) for its two doublets at 6.30 and 7.04 ppm [11]. The ratio of the Z:E isomers is found to be 2:1 from integration of the spectra recorded after 24 h of reaction.…”
Section: Resultsmentioning
confidence: 87%
“…Following the procedure for the (g 5 -C 5 Me 5 )Ru(PPh 3 )H 3 -catalyzed dimerization of terminal alkynes [11], a 5 mm NMR tube equipped with a Teflon valve (J. Youngs, Inc.) was charged with the ruthenium(II) catalyst, 0.017 mmol (g 5 -C 5 H 5 )Ru(PPh 3 ) 2 Cl or 0.022 mmol (g 5 -C 8 H 9 )Ru(PPh 3 ) 2 Cl, in an argon atmosphere. About 0.5 mL C 6 D 6 and 30 equivalents of phenyl acetylene were added.…”
Section: Dimerization Of Phenylacetylene Catalyzed By (G 5 -C 8 H 9 )mentioning
confidence: 99%
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“…A variety of ruthenium complexes containing trispyrazolyl, [131][132][133][134] P(CH 2 CH 2 PR 2 ) 3 , [126,127] N(CH 2 CH 2 PR 2 ) 3 , [135] pentamethylcyclopentadienyl, [136] indenyl, [137,138] and maltolato ligands, [139] the metathesis catalysts [RuCl 2 (PCy 3 ) 2 -(=CHPh)] [140] and [RuCl 2 (PiPr 3 ) 2 (=C=CHPh)], [141,142] as well as a dinuclear (C 5 H 5 ) 2 Ru 2 complex [143] promote the formation of Z and E enynes. Polyaddition of 2,7-diethynyl-9,9-dioctylfluorene with [RuCl 2 (PiPr 3 ) 2 ( = C = CHPh)] in the presence of N-methylpyrrolidine produces polymers containing the enynyl fragment with high Z selectivity.…”
Section: Dimerization Of Terminal Alkynesmentioning
confidence: 99%
“…[141] On the other hand, the formation of butatrienes is favored with bulky alkynes, for example, tert-butylacetylene or benzylacetylene, in the presence of catalytic precursors such as [RuH 2 (CO)(PPh 3 ) 2 ], [128] [Ru(cod)(cot)] (cot = cyclooctatriene), [128,129] or [RuH 3 (C 5 H 5 )(PCy 3 )]. [136,144] The hydrative dimerization of terminal alkynes catalyzed by [RhCl(PPh 3 ) 3 ] in the presence of a stoichiometric amount of 2-amino-3-picoline and benzoic acid (5 mol %) at 110 8C in toluene was recently reported. [145] The proposed mechanism involves the Scheme 21.…”
Section: Dimerization Of Terminal Alkynesmentioning
confidence: 99%