Synthesis, Characterization, and Norbornene Polymerization Behavior of the Half-Sandwich Complexes [Cp*3M3(μ3-L)Cl3] and [Cp*M(2-SPyH)Cl2] (M = Ir, M = Rh, [L]3−= 1,3,5-Triazine-2,4,6-trithiolato, 2-SPy = 2-Pyridinethione)

The trinuclear complexes [Cp* 3 M 3 (μ 3 -L)Cl 3 ] ( 3a, M = Ir; 3b, M = Rh; [L] 3− = 1,3,5-triazine-2,4,6-trithiolato) have been synthesized via the reactions of the bridging oxalato complexes [Cp* 2 M 2 (μ-C 2 O 4 )Cl 2 ] ( 2a, M = Ir; 2b, M = Rh) with the trisodium salt of 1,3,5-triazine-2,4,6-trithiol (Na 3 L), respectively. The reactions of half-sandwich iridium and rhodium complexes [Cp*MCl(μ-Cl)] 2 with 2-pyridinethione gave the corresponding mononuclear complexes [Cp*M(2-SPyH)Cl 2 ] ( 4a, M = Ir; 4b, M = Rh). All complexes have been characterized by elemental analyses and NMR and IR spectroscopy. The molecular structures of 3a, b and 4a, b have been determined by X-ray crystallography. The trinuclear iridium complex 3a shows catalytic activities for the polymerization of norbornene in the presence of methylaluminoxane (MAO) as cocatalyst.