The chemistry and catalytic activity of new cationic ruthenium(II) complexes in the hydrogenation of cyclohexene. Crystal structure of [RuH(CO)(PPh(3))(P(OMe)(3))(Ph(2)PCH(2)CH(2)AsPh(2))]ClO4 center dot n-C5H12

Abstract

Interaction of neutral ruthenium(II) complexes of the type [RuHCl(CO)(PPh(3)) (L-L')] [where L-L' = Ph(2)PCH(2)CH(2)PPh(2) (dppe), 1; Ph(2)PCH(2)CH(2)CH(2)PPh(2) (dppp), 2; Ph(2)PCH(2)CH(2)AsPh(2) (arphos), 3] with AgClO4 in the presence of L '' [L '' = P(OMe)(3) or PMe(3)] yielded the new cationic ruthenium(II) complexes [RuH(CO)(PPh(3))(L '') (L-L')]ClO4 [where L-L' = dppe, 4; dppp, 5; arphos, 6; L '' = PMe(3), 4; P(OMe)(3), 5 and 6]. All the complexes have been characterized by both analytical and spectroscopic (IR and H-1 NMR) methods. The structure of a cationic complex 6, [RuH(CO)(PPh(3)) (P(OMe)(3)) (arphos)]ClO4 . n-C5H12, has been confirmed by single-crystal X-ray diffraction. The Ru atom is octahedrally coordinated with CO, PPh(3) and arphos in the equatorial plane and H and P(OMe)(3) in the axial positions. In the hydrogenation of cyclohexene, some relations between structures and catalytic activities have been studied. The cationic complexes have shown lower catalytic activities than their neutral analogues.