Preparation of imine complexes of ruthenium and osmium stabilised by [MCl(η 6-p-cymene)(PR3)]+ fragments

Imine complexes [MCl(η 6-p-cymene){η1-NHC(H)Ar}(PR3)]BPh4 (1–3) [M = Ru, Os; PR3 = PPh(OEt)2, PPh2OEt; Ar = Ph, p-tolyl] were prepared by reacting MCl2(η 6-p-cymene)(PR3) precursors with benzyl azide ArCH2N3 in the presence of NaBPh4. Benzophenone-imine complexes [MCl(η 6-p-cymene){η1-NHCPh2}(PR3)]BPh4 (4–6) [M = Ru, Os; PR3 = PPh(OEt)2, PPh2OEt] were also prepared by allowing MCl2(η 6-p-cymene)(PR3) to react with Ph2CNH in the presence of NaBPh4. The complexes were characterised spectroscopically (IR, 1H, 13C, 31P, 15N NMR) and by X-ray crystal structure determination of [RuCl(η 6-p-cymene){η1-NHC(H)-p-tolyl}{PPh(OEt)2}]BPh4 (1b).

Graphical abstractThe reaction of organic azide ArCH2N3 with the half-sandwich complexes of ruthenium and osmium MCl2(η 6-p-cymene)(PR3), leading to imine derivatives [MCl(η 6-p-cymene){h1-NHC(H)Ar}-(PR3)]BPh4 (PR3 = phosphite), is described. Benzophenone-imine complexes [MCl(η 6-p-cymene)-{h1-NHCPh2}(PR3)]BPh4 are also reported.Figure optionsDownload full-size imageDownload as PowerPoint slide