摘要:
AbstractA series of closely related dinuclear (head‐head) PtII complexes of general composition cis‐[a2PtL2Pta′2]2+ with a,a′ = NH3 or CH3NH2 and L = 1‐methyluracilate‐N3,O4 (1‐MeU) or 1‐methylthyminate‐N3,O4 (1‐MeT) has been prepared and the solution behavior toward CeIV oxidation studied. The X‐ray crystal structure of a representative example cis‐[(CH3NH2)2Pt(1‐MeU)2Pt(CH3NH2)2](ClO4)2 · 0.5 H2O (1b), has been determined: Monoclinic, space group P21/c, a = 11.907(7) Å, b = 19.087(14) Å, c = 12.525(7) Å, β = 90.49(4)°, Z = 4. Oxidation of these diplatinum(II) complexes ([Pt2.0]2) with CeIV in aqueous solution to the corresponding diplatinum(III) species ([Pt3.0]2) proceeds via tetranuclear [Pt2.25]4 or dinuclear [Pt2.5]2 mixed‐valence state compounds, depending on the nature of the a′ ligands: with a′ = NH3, blue green [Pt2.25]4 forms, whereas with a′ = CH3NH2, purple [Pt2.5]2 represents the intermediate. This difference is interpreted in terms of differences in bulk between NH3 and CH3NH2 ligands trans to the O(4) positions of the bridging nucleobases which influence the ability of dinuclear species to associate via the O(4)2 Pt a2′ faces.