Synthesis of heteronuclear compounds by use of [Ti(η5-C5H4PPh2)2(SR)2](R = Et or Ph) as metalloligands. Crystal structures of [{Mo(CO)4}2{µ-(Ph2PC5H4)2Ti(SPh)2}] and [(OC)4Mo(µ-Ph2PC5H4)2Ti(µ-SPh)2Pt(C6 F5)2]

The complexes [(OC)4Mo(µ-Ph2PC5H4)2Ti(SR)2](R = Et 1 or Ph 2), [{Mo(CO)4}2{µ-(Ph2PC5H4)2Ti(SR)2}](R = Et 3 or Ph 4) and [(OC)4Mo(µ-Ph2PC5H4)2Ti(µ-SPh)2M(C6F5)2](M = Pt 5 or Pd 6) have been prepared and characterized. Complexes 1 and 2 were obtained by reaction of [Ti(η5-C5H4PPh2)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(η5-C5H4PPh2)2(SR)2] ligand.

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