Syntheses of platinum(II) complexes of cyclo-octenyl group and isolation of a self-assembled oxo-bridged macrocyclic complex [Pt4(Spy)4(C8H12-O-C8H12)2]

Reactions of [Pt-2(mu-Cl)(2)(C8H12OMe)(2)] (1) (C8H12OMe - 8-methoxy-cyclooct-4-ene-1-yl) with various anionic chalcogenolate ligands have been investigated. The reaction of 1 with Pb(Spy)(2) (HSpy = pyridine-2-thiol) yielded a binuclear complex [Pt-2(Spy)(2)(C8H12OMe)(2)] (2). A trinuclear complex [Pt-3(Spy)(4)(-C8H12OMe)(2)] (3) was isolated by a reaction between 2 and [Pt(Spy)(2)](n). The reaction of 1 with HSpy in the presence of NaOMe generated 2 and its demethylated oxo-bridged tetranuclear complex [Pt-4(Spy)(4)(C8H12-O-C8H12)(2)] (4). Treatment of 1 with ammonium diisopropyldithiophosphate completely replaced C8H12OMe resulting in [Pt(S2P{OPri}(2))(2)] (5), whereas non-rigid 5-membered chelating ligand, Me2NCH2-CH2E-, produced mononuclear complexes [Pt(ECH2CH2NMe2)(C8H12OMe)] (E = S (6), Se (7)). These complexes have been characterized by elemental analyses, NMR (H-1, C-13{H-1}, Pt-195{H-1}) and absorption spectroscopy. Molecular structures of 2, 3, 4, 5 and 7 were established by single crystal X-ray diffraction analyses. Thermolysis of 2, 6 and 7 in HDA gave platinum nanoparticles. (C) 2011 Elsevier B. V. All rights reserved.