Abstract
Protonation of the ortho-metalated ruthenium complexes RuH(H2)(X)(PiPr3)2 [X = 2-phenylpyridine (ph-py) (1), benzoquinoline (bq) (2)] and RuH(CO)(ph-py)(PiPr3)2 (3) with [H(OEt2)2]+[BAr'4]– (BAr'4 = [(3,5-(CF3)2C6H3)4B]) under H2 atmosphere yields the corresponding cationic hydrido dihydrogen ruthenium complexes [RuH(H2)(H-X)(PiPr3)2][BAr'4] [X = phenylpyridine (ph-py) (1-H); benzoquinoline (bq) (2-H)] and the carbonyl complex [RuH(CO)(H-ph-py)(PiPr3)2][BAr'4] (3-H). The complexes accommodate an agostic CFormula H interaction characterized by NMR and in the case of 1-H by x-ray diffraction. Fluxional processes involve the hydride and dihydrogen ligands in 1-H and 2-H and the rotation of the phenyl ring displaying the agostic interaction in 1-H and 3-H. NMR studies (lineshape analysis of the temperature-dependent NMR spectra) and density functional theory calculations are used to understand these processes. Under vacuum, one equivalent of dihydrogen can be removed from 1-H and 2-H leading to the formation of the corresponding cationic ortho-metalated complexes [Ru(H2)(THF)(X)(PiPr3)2]+ [X = ph-py (1-THF), bq (2-THF)]. The reaction is fully reversible. Density functional theory calculations and NMR data give information about the reversible mechanism of CFormula H activation in these ortho-metalated ruthenium complexes. Our study highlights the subtle interplay between key ligands such as hydrides, {sigma}-dihydrogen, and agostic bonds, in CFormula H activation processes.