Acylruthenium Complexes from Reactions of RuCl₂(PPh₃)₃ with Terminal Alkynes

Abstract

Reactions of 1‐phenylethyne HC≡C−Ph and 1‐octyne HC≡C‐(CH2)5CH3 with RuCl2(PPh3)3 (1) were carried out in the presence of concentrated HCl aqueous solution, and new acyl complexes Ru(=C=CHPh)(‐C(=O)CH2Ph)Cl(PPh3)2 (2) and Ru(‐C(=O)(CH2)6CH3)Cl(CO)(PPh3)2 (3) are isolated. Further decarbonylation produces Ru(‐C(CH2Ph)=CHPh)Cl(CO)(PPh3)2 (4) and RuHCl(CO)2(PPh3)2 (5), respectively. These are the first examples of stoichiometric anti‐Markovnikov hydration of terminal alkynes involving complexes without polydentate ligands.

1-Butyl-3-methylimidazolium tetrafluoroborate as suitable solvent for BF3: the case of alkyne hydration. Chemistry vs electrochemistry

“…However, the toxicity and the environmental issues associated with the use of mercury-based compounds have stimulated the search for alternative catalysts and conditions for the hydration of alkynes, in order to identify safer and more sustainable methods [11][12][13]. In particular, transitionmetal catalysts containing Au(I) or (III) [14][15][16][17][18][19][20][21][22][23][24], Ru(II) [25][26][27][28][29][30], Pd(II) [31][32][33], Pt(II) [34,35], Fe(III) [36,37], Cu(I) [38][39][40][41], Co(III) [42][43][44], as well as other metals, have been widely studied. In addition, methods involving Brønsted acids, alone or in presence of Lewis acids as co-catalysts, have been developed [45][46][47][48][49][50][51][52][53][54].…”