Copper Complexes of Silicon Pyridine-2-olates RSi(pyO)3 (R = Me, Ph, Bn, Allyl) and Ph2Si(pyO)2

The organosilicon pyridine-2-olates 1a–1d (RSi(pyO)3, R = Me (a), Ph (b), Bn (c), Allyl (d); pyO pyridine-2-olate) may serve as tripodal ligands toward CuCl with formation of complexes the type RSi(?2-pyO)3CuCl (2a–2d). In addition, for Allyl, more stable isomer 2d? (?O-pyO)Si(?2-pyO)2(?2-Allyl)CuCl was observed. presence dry air (as a source oxygen), reactions and afforded Cu(II) RSi(?2-pyO)4CuCl (3a–3d); 3a–3c in good yield, 3d only side product. Reaction Ph2Si(pyO)2 (4) equimolar ratio afforded, depending on reaction conditions, series (CuCl)n-ladder-type oligonuclear Cu(I) Ph2Si(?2-pyO)2(CuCl)n(?2-pyO)2SiPh2 (n 2 (52), 3 (53), 4 (54)). all above compounds, group is Si–O bound and, case ?2 coordination, Cu–N bound. All new compounds (1c, 1d, 2b, 2c, 2d, 2d?, 3b, 3c, 3d, 52, 53, 54) were characterized by single-crystal X-ray diffraction, further characterization includes solution 1H, 13C, 29Si NMR spectroscopy 2d’, 54), solid-state (2b, 63Cu (2c, 2d?) well computational analyses isomerization couple 2d?.