COORDINATION-COMPOUNDS OF TERT-BUTYLIMINO VANADIUM(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 irreversi ble cleavage of ether in the coordination sphere of the vanadium atom rearranging in omega-chloroalkanolato ligands are observed. The reacti on of 1 with 2-chloroethanol, 3-chloropropanol and 5-chloropentanol yi elds the complexes (C4H9N)-C-1 = V(OR)Cl-2 (R = CH2CH2CH2CH2CH2Cl) and [C4H9N = V(OR)Cl-2 . ROH]; in the presence of triethylamine the disub stituted compounds (C4H9N)-C-t = V(OR)(2)Cl are formed. The V-51 NMR s pectra are discussed. The crystal structure of [(C4H9N)-C-t = VCl3 . D ME] (12) and [(C4H9N)-C-t = V(OCH2CH2Cl)Cl-2 . HOCH2CH2Cl] (13) has be en determined. The vanadium atoms in 13 have a distorted octahedral co ordination and are linked by the oxygen atoms of the 2-chloroethanolat o ligands forming a binuclear complex. In solution molecular weight me asurement and V-51 NMR data indicate the equilibrium between a mononuc lear complex 13 and its isomer [(C4H9N)-C-t = V(OCH(2)CH(2)C1)(2)Cl . HCl].