Te2(C6H5)2 undergoes reaction with [{PtX(CH3)3}4] (X = Br, I) in chloroform solution to yield the bimetallic products [{PtX(CH3)3}2{Te2(C6H5)2}]. These complexes have been characterized by elemental analysis and low temperature multi-element (1H, 13C, 125Te, 195Pt) NMR studies. [{PtCl(CH3)3}4] was unreactive towards Te2(C6H5)2, and similarly Se2(C6H5)2 and S2(C6H5)2 failed to bring about the fission of the tetranuclear [{PtX(CH3)3}4] (X = Cl, Br, I) molecule. [{PtI(CH3)3}2{Te2(C6H5)2}] was found to be fluxional over the temperature range −20 to +65°C, and a dynamic NMR study of the complex revealed two different modes of fluxionality. The lower energy process has been ascribed to the concerted/correlated double inversion of the coordinated tellurium atoms (ΔG‡ = 59.7 ± 0.1 kJ mol−1), and the higher energy fluxion (ΔG‡ = 64.5 ± 0.03 kJ mol−1) is attributed to an intermetallic ligand commutation of the two tellurium atoms between the two platinum atoms, leading to exchange of the three platinum methyl environments.