om800861g_si_001.cif (48.96 kB)

Butenynyl and Vinylidene Complexes of Ruthenium

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posted on 22.12.2008, 00:00 by Leslie D. Field, Alison M. Magill, Paul Jensen
Reaction of ruthenium bis-acetylide complexes with 2,6-lutidinium tetrafluoroborate gave butenynyl complexes cis-[Ru(η3-RCCCC(H)R)(PMe3)4]BF4 in moderate to good yields. The structure of cis-[Ru(η3-tBuCCCC(H)tBu)(PMe3)4]BF4 was determined crystallographically. Attempts to prepare cis-[Ru(η3-MeCCCC(H)Me)(PMe3)4]BF4 resulted in the formation of two isomers, which differ in the stereochemistry about the double bond. The reaction of two bis-acetylide complexes with methyl triflate afforded butenynyl-type complexes cis-[Ru(η3-RCCCC(Me)R)(PMe3)4]+ (R = Me, Ph). The mixed acetylide−vinylidene complex trans-[Ru(CCSiMe3)(CCH2)(PMe3)4]PF6 was prepared by the reaction of trans-Ru(CCSiMe3)2(PMe3)4 with ammonium hexafluorophosphate. In addition, the crystal structure of trans-[Ru(CCH)(CCH2)(PMe3)4]BF4 is reported.