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Donor-stabilized silyl cations. 10. Pentacoordinate siliconium-ion salts with a triphenylphosphinimino-N ligand group: Two-bond P-N-Si coupling as a measure for coordination strength
, I. Kalikhman, E. Kertsnus, A.A. Korlyukov, D. Kost
Published in
Volume: 25
Issue: 15
Pages: 3665 - 3669
A new donor group, triphenylphosphinimino, is described as a ligand in pentacoordinate siliconium halide dichelates, [XSiL2] +hal-, where L is the bidentate ligand -OC(CH 2Ph)=NN(=PPh3)-, X = Me, C6H11, i-Bu, CH2C1, CHCl2, Cl, Br, and hal = Cl, Br. The complex 16 (X = Me, hal = Cl) was characterized by crystal structure analysis, and the others were characterized by NMR spectroscopy and elemental analysis. The phosphinimino ligand is a stronger donor than previously studied dimethylamino and isopropylidenimino ligands, causing all of the complexes to be pentacoordinate siliconium-halide salts in the crystal as well as in solution. Two-bond 31P-N-29Si coupling constants across the N→Si dative bond increase with increasing monodentate-ligand electron-withdrawing power and may serve as a criterion for coordination strength. © 2006 American Chemical Society.
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