Two Nearly Isoformular Isomeric Dinuclear Platinum(II) Complexes with Planar and Butterfly [Pt2(μ2-S)2] Core Structures

Abstract

Two dinuclear PtII complexes bearing fluorinated phosphine and thiolate ligands were synthesized from mononuclear starting materials, and characterized. Complex [(PPh2(C6F5))(SC6F5)Pt(μ2-SC6F5)2Pt(SC6F5)(PPh2(C6F5))] has phospine ligands arranged trans and presents a planar [Pt2(μ2-S)2] core structure, imposed by symmetry. In contrast, the almost isoformular complex [(PPh(C6F5)2)(SC6F5)Pt(μ2-SC6F5)2Pt(SC6F5)(PPh(C6F5)2)] revealed to be a butterfly molecule with phosphine ligands in a cis configuration. In both complexes, two pentafluorobenzenethiolate ligands bridge metal centers in an anti conformation. Both compounds have been X-ray characterized. Trans complex: a = 11.8576(13) A, b = 12.3237(14) A, c = 13.4644(16) A, α = 90.528(9)°, β = 113.866(9)°, γ = 107.698(9)°, $$ P\,\bar 1 $$ ; cis complex: a = 24.368(2) A, b = 15.043(2) A, c = 37.596(7) A, β = 93.69(1)°, C2/c. Two Nearly Isoformular Isomeric Dinuclear Platinum(II) Complexes with Planar and Butterfly [Pt 2 (μ 2 -S ) 2 ] Core Structures Sylvain Bernes, Luis Villanueva & Hugo Torrens Two dinuclear PtII complexes bearing fluorinated phosphine and thiolate ligands were X-ray characterized, [(PPh2(C6F5))(SC6F5)Pt(μ2-SC6F5)2Pt(SC6F5)(PPh2(C6F5))] and [(PPh(C6F5)2)(SC6F5)Pt(μ2-SC6F5)2Pt(SC6F5)(PPh(C6F5)2)]. The [Pt2(μ2-S)2] core is constrained by symmetry to be planar in the former complex, affording a trans arrangement for non-bridging ligands, whereas the latter is a butterfly molecule with a cis configuration.