Lead(II) complexes with phosphorylthiolato and thiophosphorylthiolato ligands

Neutral lead complexes of a series of phosphorylarenethiol and thiophosphor ylarenethiol proligands have been synthesised. Compounds [Pb{2-(Ph2P)C6H4S} (2)] 1, [Pb{2-(Ph2P)-6-(Me3Si)C6H3S}(2)] 2 and [Pb{2-(Ph2PO)-6-(Me3Si)C6H3S }(2)] 3 were obtained by the electrochemical oxidation of a lead anode in a cell containing an acetonitrile solution of the ligand. [Pb{2-(Ph2P(O)CH2) C6H4S}(2)] 4, [Pb{2-(Ph2P(S)CH2)C6H4S}(2)] 5 and [Pb{2,6-(Ph2P(S)CH2)(2)C6H 3S}(2)] 6 were obtained by addition of the appropriate proligand to a metha nol solution of lead acetate. The molecular structures of 3, 4 and 5 show t he metal in a five-coordinate geometry with the stereochemically active lon e pair on Pb(II) in an equatorial position of a trigonal bipyramid. In 3, t he metal coordination is supplemented by an additional weak Pb-(eta(6)-C6H6 ) intermolecular interaction with a phenyl ring from a neighbouring molecul e. Compound 6 consists of monomeric neutral molecules with the lead atom in a pseudo trigonal-bipyramidal geometry and additional weak intramolecular coordination with two sulfur atoms.