The synthesis and characterization of platinum monodithiolene complexes containing 1,3-dithiole-2-oxo-4,5-dithiolate (dmid2-) and 1,3-dithiole-2-thione-4,5-dithiolate (dmit2-)

Article abstract of DOI:10.1016/S0020-1693(98)00244-8

The platinum monodithiolene complexes (COD)Pt(dmid) (1), (COD)Pt(dmit) (2), (Ph₃P)₂Pt(dmid) (3) and (Ph₃P)₂Pt(dmit) (4) (where COD=1,5-cyclooctadiene, dmid=1,3-dithiole-2-oxo-4,5-dithiolate, dmit=1,3-dithiole-2-thione-4,5-dithiolate) have been synthesized and characterized. We report here their ¹H NMR, ¹⁹⁵Pt NMR, UV-Vis spectra and electrochemistry. The X-ray crystal structures are also reported. 2: orthorhombic, Cmcm, a=10.8535(6), b=16.8503(7), c=7.3622(3) A, Z=4. 3: triclinic, P1, a=11.2051(4), b=11.4409(5), c=15.2212(9) A, α=71.882(4), β=73.125(4), γ= 84.589(6)°, Z=2. 4·CHCl₃: triclinic, P1, a=10.2521(5), b=13.9387(14), c=15.6884(18) A, α=67.154(9), β=89.380(15), γ=83.570(13)°, Z=2. The crystal structure of 2 exhibits a molecular stacking pattern which has alternating Pt and S(thione) atoms forming a one-dimensional chain which suggests the presence of a weak axial interaction between the Pt and S(thione). A correlation exists between the ¹⁹⁵Pt NMR chemical shifts and the one-electron oxidation potentials of these complexes. In addition, it is shown that the carbonyl of the dmid^2- ligand is not susceptible to alkoxide attack when coordinated to platinum.