New complexes of functionalised ligands bearing P/N/Se or P2Se donor sets

The new selenoether functionalised tertiary phosphines (2-Ph2P)C6H4C(H) = N(CH2)(n)SePh (n = 3 1a; 4 1b) were readily prepared by condensation of (2-Ph2P)C6H4C(H)=O and H2N(CH2)(n)SePh (n = 3, 4) in absolute ethanol. Reaction of two equiv. of Ph2PCH2OH with H2N(CH2)(n)SePh (n = 3, 4) affords the symmetrical ditertiary phosphines (Ph2PCH2)(2)N(CH2)(n)SePh (n = 3 2a; 4 2b). Reaction of 1a 2b with [MCl2(cod)] (M = Pt, Pd) gave the dichlorometal(II) chelate complexes 3a-4d in which either six-membered P,P- or P,N-ligation is observed. Chloro bridge cleavage of [{RuCl2(p-cymene)}(2)] or tht (tht = tetrahydrothiophene) substitution of [AuCl(tht)] with 2a (or 2b) gave the new complexes [{RuCl2(p-cymene)}(2) {mu-(P,P'-Ph2PCH2)(2)N(CH2)(n)SePh}] (n = 3 5a; 4 5b) or [{AuCl}(2){mu-(P,P'-Ph2PCH2)(2)N(CH2)(n)SePh}] (n = 3 6a; 4 6b) in which the ligand P,P'-bridges two metal centres. Spectroscopic evidence suggests the pendant selenoether group in 3c undergoes further reaction with [PdCl2(MeCN)(2)] affording an unusual trinuclear palladium( II) complex 7. Furthermore reaction of 3b with 1 equiv. of Ag[BF4] in dichloromethane gave the cationic complex [ PtCl(1a)][BF4] 8 in which 1a functions as a P,N,Se-tridentate ligand. All structures have been confirmed by a combination of spectroscopic, analytical and single crystal X-ray studies. The structure of 8 represents, to the best of our knowledge, an extremely rare example of a crystallographically characterised Group 10 metal complex with a P/N/Se/Cl coordination environment.