Arene and Hydride Complexes of Ruthenium with fac PSiP Pincer Ligands

Abstract

AbstractSeveral derivatives of the dinuclear complex [Ru(μ‐Cl){κP, P,Si‐Si(Me)(C6H4‐2‐PiPr2)2}]2 (1) are described. The mononuclear cationic arene complex [Ru{κP, P,Si‐Si(Me)(C6H4‐2‐PiPr2)2}(η6‐C6H6)](CF3SO3) (5), the phosphane adduct [Ru{κP, P,Si‐Si(Me)(C6H4‐2‐PiPr2)2}Cl(PPh3)] (2), and the hydride‐bridged dinuclear derivatives [Ru2(μ‐Cl)(μ‐H){κP, P,Si‐Si(Me)(C6H4‐2‐PiPr2)2}2] (6) and [Ru2(μ‐H){κP, P,Si‐Si(Me)(C6H4‐2‐PiPr2)2}]2 (7) retain the fac coordination mode of the κP, P,Si ligand present in the precursor complex. In contrast, the neutral and cationic acetonitrile derivatives [Ru{κP, P,Si‐Si(Me)(C6H4‐2‐PiPr2)2}Cl(NCMe)2] (3) and [Ru{κP, P,Si‐Si(Me)(C6H4‐2‐PiPr2)2}(NCMe)3](CF3SO3) (4), respectively, show the PSiP pincer coordinated in the more usual mer fashion. Crystal structures determined by X‐ray diffraction are shown for complexes 5, 6, and 7. The factors that influence the choice of coordination mode for the PSiP ligand are discussed.