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 [Pt2(μ-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 [Pt2(Spy)2(C8H12OMe)2] (2). A trinuclear complex [Pt3(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 [Pt4(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, Me2NCH2CH2E−, produced mononuclear complexes [Pt(ECH2CH2NMe2)(C8H12OMe)] (E = S (6), Se (7)). These complexes have been characterized by elemental analyses, NMR (1H, 13C{1H}, 195Pt{1H}) 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.

The reaction of [Pt2(μ-Cl)2(C8H12OMe)2] (C8H12OMe = 8-methoxy-cyclooct-4-ene-1-yl) with anionic chalcogenolate ligands yields a variety of platinum complexes. A unique demethylated oxo-bridged tetranuclear complex [Pt4(Spy)4(C8H12-O-C8H12)2] has been isolated and structurally characterized. Thermolysis of these complexes in HDA gave platinum nanoparticles.Figure optionsDownload as PowerPoint slideHighlights
► Pt(II) complexes with weak octenyl group and strong chalcogenolate ligand were synthesized and structurally characterized.
► A new oxo-bridged tetranuclear macrocyclic Pt(II) complex [Pt4(Spy)4(C8H12-O-C8H12)2] has been structurally characterized.
► Binuclear Pt(II) complexes with pyridine-2-thiolate ligand exist as two isomeric forms.
► Platinum complexes containing strong Pt–E (E = S or Se) bond after pyrolysis yield platinum nanoparticles rather than PtE.