Synthesis and structure of new compounds with Pt–Ga bonds: Insertion of the bulky gallium (I) bisimidinate Ga(DDP) into Pt–Cl bond

Reactions of the sterically bulky mono-valent group 13 bisimidinate gallium(I), Ga(DDP) (1) (DDP = 2-{(2, 6-diisopropylphenyl)amino}-4-{(2, 6-diisopropylphenyl)imino}-2-pentene, HC(CMeNC6H3-2,6-iPr2)2) with olefin supported group 10 complexes, [(diene)PtCl2] [diene = 1,5-cyclooctadiene (COD), endo-dicyclopentadiene (dcy)] and [(COD)Pd(Me)(OTf)] (OTf = O3SCF3) are reported. These reactions afforded [(COD)Pt(Cl){ClGa(DDP)}] (2), [(dcy)Pt(Cl){ClGa(DDP)}] (3) and [(DDP)Ga(Me)(OTf)] (4) in moderate yields. Compounds 2–4 were characterized by elemental analysis, NMR (1H, 13C) spectroscopy and also by single crystal X-ray structural analysis. The solid state structures of complexes 2 and 3 reveal the oxidative insertion of Ga(DDP) into the Pt–Cl bond without altering the π-coordinated double bonds in the olefin.

Reactions of the low valent gallium (I) β-diketiminate, GaI(DDP) with olefin supported dichloro platinum(II) and palladium (II) complexes have been studied. Insertion of the bulky GaI(DDP) into the Pt–Cl bonds are achieved without substituting the olefins on the platinum centre.Figure optionsDownload as PowerPoint slideHighlights
► Low valent main-group metal (I) carbenoid gallium (I), Ga(DDP) reacts with olefin supported Pt(II) complexes.
► Neutral gallium (I), Ga(DDP) selectively inserts into the Pt–Cl bonds.
► New complexes with Pt–Ga bonds.