title: Ambient-Temperature Synthesis of 2-Phosphathioethynolate, PCS-, and the Ligand Properties of ECX-(E = N, P; X = O, S).
abstract: A synthesis of the 2-phosphathioethynolate anion, PCS-, under ambient conditions is reported. The coordination chemistry of PCO-, PCS-and their nitrogen-containing congeners is also explored. Photolysis of a solution of W(CO)6in the presence of PCO-[or a simple ligand displacement reaction using W(CO)5(MeCN)] affords [W(CO)5(PCO)]-(1). The cyanate and thiocyanate analogues, [W(CO)5(NCO)]-(2) and [W(CO)5(NCS)]-(3), are also synthesised using a similar methodology, allowing for an in-depth study of the bonding properties of this family of related ligands. Our studies reveal that, in the coordination sphere of tungsten(0), the PCO-anion preferentially binds through the phosphorus atom in a strongly bent fashion, while NCO-and NCS-coordinate linearly through the nitrogen atom. Reactions between PCS-and W(CO)5(MeCN) similarly afford [W(CO)5(PCS)]-; however, due to the ambidentate nature of the anion, a mixture of both the phosphorus- and sulfur-bonded complexes (4aand4b, respectively) is obtained. It was possible to establish that, as with PCO-, the PCS-ion also coordinates to the metal centre in a bent fashion.
authors.affiliation: Department of Chemistry, University of Oxford, Chemistry Research Laboratory 12 Mansfield Road, Oxford OX1 3TA, UK, http://research.chem.ox.ac.uk/jose-goicoechea.aspx.
authors.forename: Andrew R
authors.initials: AR
authors.lastname: Jupp
authors.affiliation: Department of Chemistry, University of Oxford, Chemistry Research Laboratory 12 Mansfield Road, Oxford OX1 3TA, UK, http://research.chem.ox.ac.uk/jose-goicoechea.aspx.
authors.forename: Michael B
authors.initials: MB
authors.lastname: Geeson
authors.affiliation: Department of Chemistry, University of Oxford, Chemistry Research Laboratory 12 Mansfield Road, Oxford OX1 3TA, UK, http://research.chem.ox.ac.uk/jose-goicoechea.aspx.
authors.forename: John E
authors.initials: JE
authors.lastname: McGrady
authors.affiliation: Department of Chemistry, University of Oxford, Chemistry Research Laboratory 12 Mansfield Road, Oxford OX1 3TA, UK, http://research.chem.ox.ac.uk/jose-goicoechea.aspx.
authors.forename: Jose M
authors.initials: JM
authors.lastname: Goicoechea
keywords: Coordination modes; Cyanates; Ligand effects; P ligands; Thiocyanates