Synthesis of heteronuclear compounds by use of [Ti(eta(5)-C(5)H(4)PPh(2))(2)(SR)(2)] (R=Et or Ph) as metalloligands. Crystal structures of [{Mo(CO)(4)}(2){mu-(Ph(2)PC(5)H(4))(2)Ti(SPh)(2)}] and [(OC)(4)Mo(mu-Ph(2)PC(5)H(4))(2)Ti(mu-SPh)(2)Pt(C6F5)(2)]

The complexes [(OC)(4)Mo(mu-Ph(2)PC(5)H(4))(2)Ti(SR)(2)] (R = Et 1 or Ph 2), [{Mo(CO4)}(2){mu-(Ph(2)PC(5)H(4))(2)Ti(SR)(2)}] (R = Et 3 or Ph 4) and [(OC)(4)Mo(mu-Ph(2)PC(5)H(4))(2)Ti(mu-SPh)(2)M(C6F5)(2)] (M = Pt 5 or Pd 6) have been prepared and characterized. Complexes 1 and 2 were obtained by reaction of [Ti(eta(5)-C(5)H(4)PPh(2))(2)(SR)(2)] and [Mo(CO)(4)(nbd)] (nbd = norbornadiene) in 1:1 molar ratio by replacement of the nbd by two cyclopentadienyldiphenylphosphines co-ordinated by the P atoms. The ability of the S atoms in the thiolate ligands to act as Lewis bases leads to a further increase in nuclearity. Thus, when the reaction was carried out in a 1 :3 molar ratio, heterotrinuclear complexes 3 and 4 were obtained. The crystal structure of 4 showed that the titanium mononuclear compound acts as a symmetric S,P-bridging tetradentate ligand towards two Mo(CO)(4) fragments. Compound 2 reacted with cis-[M(C6F5)(2)(thf)(2)](M = Pt or Pd, thf tetrahydrofuran) to give 5 and 6, respectively. The crystal structure of 5 showed that 2 acts as an S,S-bidentate metalloligand towards the M(C6F5)(2) fragment. It is remarkable that both structures reveal a different co-ordination mode of the tetradentate [Ti(eta(5)-C(5)H(4)PPh(2))(2)(SR)(2)] ligand.