Cyclometallated imine complexes with oxygen-functionalised side-chains: Effect of the nature of the functional group, chain length and charge on coordination of the oxygen

Imines 1a–e derived from benzaldehyde or 3,4-dimethoxy benzaldehyde and ether- or alcohol-functionalised amines H2NR (R = C2H4OMe, C3H6OMe, C2H4OH, C3H6OH,) all undergo cyclometallation with [Pd(OAc)2]3 (in some cases the dimeric products 2 were isolated) and subsequently react with lithium chloride to give chloride complexes, which are dimeric 3a–c, or monomeric for the C3H6OH-functionalised complexes 4d,e which have a C,N,O tridentate imine. The chloride complexes subsequently react with triphenylphosphine, and in some cases pyridine, to give mononuclear complexes 5 and 6, respectively with bidentate C,N imines. Treatment of 5 with silver salts leads to cations, the length of the tether (C2 or C3) and nature of the donor (ether or alcohol) and the counterion all effect whether or not the oxygen is coordinated.

Graphical abstractCyclopalladated imines containing oxygen-functionalised side-arms were synthesised and fully characterised. The length of the tether, nature of the functional group (R = H, Me) and the nature of the other ligands X,Y and charge on the complex all affect whether the oxygen atom is coordinated or not.Figure optionsDownload full-size imageDownload as PowerPoint slide