Komplexbildung des tert-Butyliminovanadium(V)-trichlorids mit O-Donor-Liganden

Coordination Compounds of tert-Butyliminovanadium(V) Trichloride with O-Donor-Ligands The reaction of tert-butyliminovanadium(V)trichloride ( 1 ) with cyclic and acyclic ethers, ethylene carbonate and thietane has been studied. The 1:1-complexes have a different stability; reversible and irreversible cleavage of ether in the coordination sphere of the vanadium atom rearranging in ω-chloroalkanolato ligands are observed. The reaction of 1 with 2-chloroethanol, 3-chloropropanol and 5-chloropentanol yields the complexes ^tC₄H₉N = V(OR)Cl₂ (R = CH₂CH₂CH₂CH₂CH₂Cl) and ^tC₄H₉N = V(OR)Cl₂ · ROH]; in the presence of triethylamine the disubstituted compounds ^tC₄H₉N = V(OR)₂Cl are formed. The ⁵¹V NMR spectra are discussed. The crystal structure of ^tC₄H₉N = VCl₃ · DME] ( 12 ) and ^tC₄H₉N = V(OCH₂CH₂Cl)Cl₂ · HOCH₂CH₂Cl] ( 13 ) has been determined. The vanadium atoms in 13 have a distorted octahedral coordination and are linked by the oxygen atoms of the 2-chloroethanolato ligands forming a binuclear complex. In solution molecular weight measurement and ⁵¹V NMR data indicate the equilibrium between a mononuclear complex 13 and its isomer ^tC₄H₉N = V(OCH₂CH₂Cl)₂Cl · HCl].