Platinum Complexes of Naphthalene‐1,8‐dichalcogen and Related Polyaromatic Hydrocarbon Ligands

Platinum bisphosphine complexes bearing dichalcogen-derivatised naphthalene, acenaphthene or phenanthrene ligands have been prepared by either oxidative addition to zero-valent platinum species or from [PtCl(2)(PPhR(2))] (R=Ph or Me) and the disodium or dilithium salts of the parent disulfur, diselenide or mixed S/Se species. The parent naphthalene, acenaphthene and phenanthrene chalcogen compounds were treated with either [Pt(PPh(3))(4)] or [Pt(C(2)H(4))(PMe(3))(2)] (prepared in situ from [PtCl(2)(PMe(3))(2)], ethene and sodium naphthalide or super hydride [LiBEt(3)H]) to give the appropriate platinum(II) species. The dilithium salts of 1,8-E(2)-naphthalene (E=S or Se) prepared in situ by reduction of the E-E bond with [LiBEt(3)H] were treated with [PtCl(2)(PPh(3))(2)] to give [Pt(1,8-E(2)-nap)(PPh(3))(2)]. The tetraoxides [Pt(1,8-(S(O)(2))(2)-nap)(PR(3))(2)] (PR(3)=PPh(3) or PMe(2)Ph) were prepared in a similar metathetical manner from the appropriate [PtCl(2)(PR(3))] complexes and the disodium salt of naphthalene 1,8-disulfinic acid (1,8-(S(O)ONa)(2)-nap). The X-ray structures of selected examples reveal bidentate coordination with the naphthalene-E(2) unit hinged (111-137 degrees) with respect to the coordination plane. The naphthalene ring suffers significant distortion from planarity.