Ruthenium vinylidene and carbyne complexes containing a multifunctional tridentate ligand with a PNN donor set

The neutral, octahedral ruthenium vinylidene complexes mer,trans-[(PNN)Cl2Ru(CCHR)] (PNN = N-(2-diphenylphosphinobenzylidene)-2-(2-pyridyl)ethylamine; R = Ph, 1a; R = tBu, 1b) are reported. An X-ray crystallographic study of 1a confirms the tridentate, meridional coordination mode of the PNN ligand. Compounds 1a and 1b undergo regioselective electrophilic addition with HBF4 · Et2O at Cβ of the vinylidene ligand at low temperatures, and are cleanly and quantitatively converted to the ruthenium carbynes mer,trans-[(PNN)Cl2Ru(CCH2R)][BF4] (R = Ph, 2a; R = tBu, 2b). Carbynes 2a and 2b are stable only at low temperatures (<−50 °C). Complex 1a undergoes ligand substitution with L to yield mer,trans-[(PNN)Cl2Ru(L)] (L = MeCN, 3a; L = CO, 3b).