Synthesis of the complexes (π-C5H5)Ru(L)2Cl [L = PPh3, PPh2Me, P(OMe)3, AsPh3] and the related osmium compound (π-C5H5)Os(PPh3)2Br are described. Reactions of (π-C5H5)Ru(PPh3)2Cl of three types were investigated: (a) replacement of the Cl atom by, e.g. H, Me, C6F5, or SnCl3 groups; (b) replacement of one of the phosphine ligands by, e.g. CO, PPh2Me; (c) formation of cationic complexes of the type [(π-C5H5)Ru(PPh3)2L]+, e.g. L = CO, MeCN. Two unusual complexes, (π-C5H5)Ru(PPh3)2BH4, and the hexachlorodizincate, [(π-C5H5)-Ru(PPh3)2(MeCN)]2Zn2Cl6, are also reported.