SOLUBLE NI-II ALKOXIDES BASED ON DIMETHYLAMINOISOPROPOXIDE LIGANDS - MOLECULAR-STRUCTURE OF [LI(PR-IOH)NI(ETA(2)-OR)(2)CL](2) AND OF CIS-NICL2(ROH)(2) (R=CHMECH2NME2)

Various routes to Ni-II-aminoalkoxides have been investigated. A nicke l isopropoxide derivative 1 was prepared by anodic dissolution of the metal in the presence of LiCl as electrolyte. Alcoholysis reactions of 1 with 1-dimethylamino-2-propanol afforded the homoleptic nickel(II) aminoalkoxide 2 together with a Ni-Li species 3. 2 was also obtained b y metathesis reactions between sodium alkoxide and the nickel hexammin e complex whereas the reaction between the latter and the aminoalcohol led to an halide solvate, cis-NiCl2(eta(2)-ROH)(2), 4. The various co mpounds were characterized by elemental analysis, FT-IR and UV-vis spe ctroscopies as well as by X-ray diffraction for 3 and 4. 3 corresponds to [Li((PrOH)-O-i)Ni(eta(2)-OCHMeCH2NMe2)Cl](2) and the overall struc ture can be seen as two [Ni(eta(2)-OCHMeCH2NMe2)(2)Cl](-) moieties ass embled by Li((PrOH)-O-i)(+). The lithium atom is 4-coordinate due to i ts interaction with the oxygen atoms of the aminoalkoxide ligands. Nic kel is 5-coordinate with a distorted tetragonal pyramidal stereochemis try, one nitrogen being in the apical position. The metal displays a d istorted octahedral surrounding for the NiCl2 adduct 4. The bond dista nces vary in the order Ni-OR < Ni-N approximate to Ni-O(H)R < Ni-Cl fo r 3 and 4. The various compounds (except 1) are soluble in organic med ia. (C) 1997 Elsevier Science Ltd.