Synthesis and characterisation of [(η6-cymene)Ru(L)X2] compounds:: single crystal X-ray structure of [(η6-cymene)Ru(P{OPh}3)Cl2] at 203 K

Treatment of the chloro bridged dimer {[(eta(6)-cymene)RuCl](2)(mu-Cl)(2)} (1) with the donor molecules P(OPh)(3), P(OMe)(3), PPh3, PMe3, CO, SMe2, (CNBu)-Bu-t and CNTos in hot hexane causes bridge splitting reactions that produce the monomeric compounds [(eta(6)-cymene)Ru(L)Cl-2], (4)-(11), respectively. Use of the chiral isonitrile S(-)-alpha-methylbenzylisonitrile produced the corresponding complex 12. The diiodo analogues, 13-15, were prepared similarly from {[(eta(6)-cymene)RuI](2)(mu-I)(2)} (3) for P(OPh)(3), P(OMe)(3) and PPh3, respectively. Insertion of tin(II) chloride into both metal-chlorine bonds was observed for [(eta(6)-cymene)Ru(P{OMe}(3))Cl-2] (5), while only monosubstitution was observed for [(eta(6)-cymene)Ru(PPh3)Cl-2] (6). Halide abstraction in the presence of a substrate reaction has been used to prepare some selected cationic compounds which contain an asymmetric ligand environment. Reaction of {[(eta(6)-cymene)RuCl](2)(mu-Cl)(2)} with 1,2-bis(diphenylphosphino)-ethane under ionising conditions produced the cation [(eta(6)-cymene)Ru(dppe)Cl]PF6 (20). Selected compounds have been examined by {C-13-H-1} heteronuclear correlation and {H-1-H-1} COSY and NOESY experiments. The structure of [(eta(6)-cymene)Ru(P{OPh}(3))Cl-2](CH2Cl2)-C-. (4) has been determined at -70degreesC. (C) 2004 Elsevier Ltd. All rights reserved.