1-Ethynyl-2,3,4,5-tetramethylruthenocene was prepared by the reaction of 1-formyl-2,3,4,5-tetramethylruthenocene with trimethylsilyldiazomethyllithium and also by the reaction of 1-(2‘,2‘-dichlorovinyl)-2,3,4,5-tetramethylruthenocene, which was obtained from the reaction of 1-formyl-2,3,4,5-tetramethylruthenocene with lithium dichloromethyldiethylphosphonate and tert -butyllithium in good yield. 1-Ethynyl-2,3,4,5-tetramethylruthenocene reacted with RuCl P 2 L ( P 2 = 2 PPh 3 or dppe; L = η-C 5 H 5, η-C 5 Me 5, or η 5 -C 9 H 7 ) in the presence of NH 4 PF 6 or AgBF 4, followed by the column chromatography on deactivated Al 2 O 3, to give Ru(C⋮CRc‘) P 2 L in moderate or good yield. Ru(C⋮CRc) P 2 (η 5 -C 9 H 7 ) and Ru(C⋮CRc*) P 2 (η 5 -C 9 H 7 ) were similarly prepared (Rc, Rc‘, and Rc* are ruthenocenyl, 2,3,4,5-tetramethylruthenocenyl, and 1‘,2‘,3‘,4‘,5‘-pentamethylruthenocenyl, respectively). The structures of Ru(C⋮CRc‘)(dppe)(PPh 3 ) 2 (η-C 5 H 5 ), Ru(C⋮CRc)(dppe)(η 5 -C 9 H 7 ), and Ru(C⋮CRc‘)(dppe)(η 5 -C 9 H 7 ) were determined by X-ray analysis. Cyclic voltammetry of the acetylide complexes showed two well-separated quasi-reversible waves. Chemical oxidation of ruthenium(II) 2,3,4,5-tetramethylruthenocenylacetylide complexes gave products whose stability was dependent on the ligand on the Ru(II) moiety. The 13 C NMR spectrum of the oxidized species isolated as stable crystals confirmed the structural rearrangement of the bridging acetylide ligand to a μ-η 6:η 1 -[(cyclopentadienylidene)ethylidene] ligand. The structure of [(η-C 5 H 5 )Ru(μ-η 6:η 1 -C 5 Me 4 C C)Ru(dppe)(η 5 -C 5 Me 5 )](BF 4 ) 2 was determined by X-ray analysis.
No takes yet. Share an insight, caveat, or question.
Satô et al. (1999) studied this question.
Synapse has enriched 5 closely related papers on similar clinical questions. Consider them for comparative context: