Synthesis and spectroscopic properties of homo– and heterobimetallic complexes of oxovanadium (V)

Abstract

Equimolar interaction of VO(OPr i) 3 with N-phenyldiethanolamine (H 2 L) affords the dimeric complex [VO(L)(µ-OPr i)] 2 (1), which on reaction with different glycols yields a new class of oxovanadium(V) complexes of the type: VO(L)(OGOH) (where L = C 6 H 5 N(CH 2 CH 2 O-) 2 and G = G 1 (CMe 2 CH 2 CH 2 CMe 2) 2, G 2 (CHMeCH 2 CMe 2) 3, G 3 (CH 2 CMe 2 CH 2) 4, G 4 (CH 2 CEt 2 CH 2) 5, G 5 (CHMeCHMe) 6, G 6 (CMe 2 CMe 2) 7), featuring N-phenyldiethanolaminate and glycolate moieties. Complexes (2)-(7) react with Al(OPr i) 3 to afford novel heterobimetallic coordination complexes of the type: VO(L){(OGO) Al(OPr i) 2 } (G = G 1-G 6). All these complexes have been characterised by elemental analyses and molecular weight measurements. Spectroscopic (IR, UV-Vis and (1 H, 27 Al, 51 V) NMR) properties of the new complexes have been investigated and their plausible structures suggested.

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“…The bonding from phenolic oxygen to vanadium has further been indicated by the appearance of entirely new bands in the 580-520 cm −1 region ascribed to υ (V-O) mode. 18 The absorption band due to υ (V=O) mode appeared at 985 cm −1 in [VO(OC 6 H 3 (NO 2 ) 2 -2,4) 3 ] relative to that reported to occur at 1035 cm −133 in VOCl 3 and in the 1020-960 cm −1 region in a number of vanadyl salts and complexes. 34 A lowering in υ (V=O) mode may be attributed to a weakening of the V=O bond from terminal oxo oxygen pπ → vanadium dπ donation upon complexation with phenoxide ion.…”

“…16 For vanadium, the chemistry of oxovanadium(IV) and (V) ions of the type VO 2+ , VO 3+ , VO 2+ 2 , and V 2 O 4+ 3 with a variety of ligands has widely been studied. 17,18 The VO 3+ ion, in particular because of its hard acidic nature, is known to exhibit rich chemistry with oxygen and nitrogen donor ligands. Of these, vanadium phenolates have been reported to display capabilities of dinitrogen fixation 19−21 and considerable significance for polymerization, 22 oxidation, 23 and potential shape-selective transformations.…”