Abstract
The neutral, octahedral ruthenium vinylidene complexes mer, trans-[(PNN)Cl 2Ru(CCHR)] (PNN = N-(2-diphenylphosphinobenzylidene)-2-(2-pyridyl)ethylamine; R = Ph, 1a; R = t Bu, 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 HBF 4 · Et 2O at C β of the vinylidene ligand at low temperatures, and are cleanly and quantitatively converted to the ruthenium carbynes mer, trans-[(PNN)Cl 2Ru(CCH 2R)][BF 4] (R = Ph, 2a; R = t Bu, 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)Cl 2Ru(L)] (L = MeCN, 3a; L = CO, 3b).
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