Activation of terminal alkynes with Ru(II)-arene complexes

Activation of terminal alkynes was evaluated through Ru(II)-arene complexes. In particular, improvement of [RuCl(h6-C6Me6)(PPh3){=C(OMe)CH2Ph}]PF6 (1a) synthesis was carried out and new Ru-arene-alkoxycarbene complexes were synthetized with various terminal alkynes from different h6-arene complexes of ruthenium with phosphine ligands. Compound 1a reactivity was explored with various bases, HOTf and AgOTf, moreover two new Ru-arene-vinyl complexes were checked via NMR analyses. Investigation on by-products formation in 1a synthesis was fulfilled, changing most of reaction parameters. Syntheses of [RuCl(h6-C6Me6)(PPh3)(CO)]PF6 (3) and [RuCl(CCPh)(h6-arene)(PPh3)] (arene: C6Me6, p-cymene) (4a,4b) were achieved, on the contrary of [Ru(CH2Ph)(h6-C6Me6)(PPh3)(CO)]PF6 (2a) one. A series of amines and thiols were tested in attempted syntheses of Ru-arene-aminocarbene and Ru-arene-thiocarbene complexes, respectively. Other attempts regarded syntheses of [RuCl(h6-C6Me6)(PPh3)(RNH2)]PF6 (R: H, Me) (6a,6b). Synthesis and NMR characterization of new RAPTA-acetilyde derivates were performed with twelve terminal alkynes: [RuCl(CCR)(h6-arene)(PTA)] (arene: p-cymene, C6Me6) (4c-4o). Eventually, stability in deuterated aqueous medium was assessed for complexes RAPTA-C and 4c