Heterobimetallic f-d Complexes, Derivative of Fluorinated Lanthanum and Gadolinium #beta#-Diketonates and Nickel(II) and Copper(II) N,N'-Ethylenebis(acetylacetoniminate)s

摘要

Seven new heterobimetallic complexes (M(Acacen)Ln(Dik)_3) were synthesized by reacting Ln(Dik)_3 (Ln is La or Gd; HDik is hexafluoroacetylacetone (HHfa), pyvaloyltrifluoroacetylacetone (HPta), or 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dione (HFod)) with neutral M (Acacen) complexes (M is Ni(II) or Cu(II); H_2(Acacen) is the Schiff base prepared from 1 mol of ethylenediamine and 2 mol of acetylacetone). Two of these complexes were characterized by X-ray crystallography: (Ni(Acacen)Gd(Pta)_3) (space group P2_1/c, a = 10.188(1) A, b = 36.083(3) A, c = 12.529(1) A, #beta# = 110.15(1) deg, Z = 4, R_1 = 4.22 percent) and (Cu(Acacen)La(Fod)_3) (space group P2_1/c, a = 14.122(1) A, b = 20.111(2) A, c = 18.503(2) A, #beta# = 96.03(1) deg, Z = 4, R_1 = 4.13 percent). The crystal structures of both complexes are composed of heterobinuclear molecules in which M(Acacen) acts as a neutral electron-donating ligand with respect to Ln~(3+) ions. (M(Acacen)Ln(Dik)_3) molecules are linked by a system of hydrogen bonds involving fluorine and oxygen atoms. Upon heating in vacuum, the (M(Acacen)Ln(Dik)_3) complexes sublime without decomposition at temperatures of 200-240 deg C/0.01 mmHg.