Vanadium(IV/V) Complexes Containing [VO]2+, [VO]3+, [VO2]+ and [VO(O2)]+ Cores with Ligands Derived from 2-Acetylpyridine andS-Benzyl- orS-Methyldithiocarbazate

Vanadium complexes containing [VO]2+, [VO]3+, [VO2]+ and [VO(O2)]+ cores with ligands (LH) derived from 2-acetylpyridine and S-benzyldithiocarbazate (Hacpy-sbdt, I) or S-methyldithiocarbazate (Hacpy-smdt, II) are introduced. The dioxovanadium(V) complexes [VO2L] [HL = I (2), II (5)] were isolated from the reaction between LH and [VO(acac)2] in the presence of air and KOH in dry methanol. Treatment of II with aerated [VO(acac)2] in wet methanol yielded the malonato complex [VO(acpy-smdt)mal] (6), with the malonate ligand originating from acetylacetonate. Under anaerobic reaction conditions, LH replaced one of the acac(1−) ligands to yield the oxovanadium(IV) complexes [VO(acac)L] [HL = I (1), II (4)]. Treatment of these complexes with H2O2, catechol or benzhydroxamic acid gave rise to oxo(peroxo)vanadium complexes [VO(O2)L] [HL = I (3), II (7)], catecholato complexes [VOL(cat)] [HL = I (8), II (9)] or benzhydroxamato complexes [VOL(bha)] [HL = I (10), II (11)]. Compounds 3 and 7 were capable of transferring an oxo group to PPh3. In the presence of L-ascorbic acid under aerobic conditions, 8 and 11 were converted into 2 and 5, possibly through intermediate reduction. Acidification of 2 with HCl in methanol afforded a hydroxo(oxo) complex. The crystal and molecular structures of 2 and 6 were determined, confirming the NNS (enethiolate) binding mode of L−, and the bidentate coordination of the malonate ligand in 6. The geometrical arrangement of the ligand set in 2 is intermediate between a trigonal bipyramid and a tetragonal pyramid. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

[1]  A. Salifoglou,et al.  In vitro study of the insulin-mimetic behaviour of vanadium(IV, V) coordination compounds , 2002, JBIC Journal of Biological Inorganic Chemistry.

[2]  Martin Ebel,et al.  Vanadium(IV and V) Complexes Containing SNO (Dithiocarbonylhydrazone; Thiosemicarbazone) Donor Sets , 2001 .

[3]  T. Kiss,et al.  Solution speciation of bioactive Al(III) and VO(IV) complexes , 2000 .

[4]  N. Bharti,et al.  Synthesis and antiamoebic activity of new cyclooctadiene ruthenium(II) complexes with 2-acetylpyridine and benzimidazole derivatives. , 2000, Bioorganic & medicinal chemistry letters.

[5]  J. Rodríguez,et al.  Synthesis, characterization and novel crystal structure of (salicylaldehyde-4-phenylthiosemicarbazidato) ammonium dioxovanadate(V) with a VS bond , 2000 .

[6]  D. Hughes,et al.  Vanadium complexes of the N(CH2CH2S)3(3-) and O(CH2CH2S)2(2-) ligands with coligands relevant to nitrogen fixation processes. , 2000, Inorganic chemistry.

[7]  H. Sakurai,et al.  An orally active antidiabetic vanadyl complex, bis(1-oxy-2-pyridinethiolato)oxovanadium(IV), with VO(S2O2) coordination mode; in vitro and in vivo evaluations in rats. , 2000, Journal of inorganic biochemistry.

[8]  E. Baran.  Oxovanadium(IV) and oxovanadium(V) complexes relevant to biological systems. , 2000, Journal of inorganic biochemistry.

[9]  S. Pal,et al.  A dimeric pervanadyl (VO2+) complex with a tridentate Schiff base ligand , 2000 .

[10]  B. Neelam,et al.  Palladium(II) complexes of NS donor ligandsderived from S-methyl-dithiocarbazate, S-benzyldithiocarbazateand thiosemicarbazide as antiamoebic agents. , 2000, European journal of medicinal chemistry.

[11]  Susie M. Miller,et al.  Chemistry and insulin-mimetic properties of bis(acetylacetonate)oxovanadium(IV) and derivatives. , 2000, Inorganic chemistry.

[12]  H. Schoemaker,et al.  Probing the scope of the sulfoxidation activity of vanadium bromoperoxidase from Ascophyllum nodosum , 1999 .

[13]  D. Schomburg,et al.  X-ray structure determination of a vanadium-dependent haloperoxidase from Ascophyllum nodosum at 2.0 A resolution. , 1999, Journal of molecular biology.

[14]  S. Hikichi,et al.  Inter- and Intramolecular Hydrogen-Bonding Interaction of Hydroxo Groups and Steric Effect of Alkyl Substituents on Pyrazolyl Rings in TpR Ligands: Synthesis and Structural Characterization of Chloro-, Acetylacetonato-, and Hydroxo Complexes of VO2+ with TpPri2 and TpMe2 Ligands† , 1999 .

[15]  A. Evangelou,et al.  Synthetic Analogues for Oxovanadium(IV)–Glutathione Interaction: An EPR, Synthetic and Structural Study of Oxovanadium(IV) Compounds with Sulfhydryl‐Containing Pseudopeptides and Dipeptides , 1999 .

[16]  D. Rehder.  The Coordination Chemistry of Vanadium as Related to Its Biological Functions , 1999 .

[17]  A. Tracey,et al.  Vanadium Compounds: Chemistry, Biochemistry, and Therapeutic Applications , 1998 .

[18]  H. Schoemaker,et al.  Enantioselective Sulfoxidation Catalyzed by Vanadium Haloperoxidases. , 1998, Inorganic chemistry.

[19]  Shan Gao,et al.  Synthesis and characterization of two novel monooxovanadium(V) complexes with bidentate benzohydroxamate ligand , 1998 .

[20]  Shan Gao,et al.  Syntheses and characterization of four novel monooxovanadium(v) hydrazone complexes with hydroxamate or alkoxide ligand , 1998 .

[21]  S. P. Rath,et al.  A Family of (N-Salicylidene-α-amino acidato)vanadate Esters Incorporating Chelated Propane-1,3-diol and Glycerol: Synthesis, Structure, and Reaction , 1998 .

[22]  S. P. Rath,et al.  Synthesis and structure of vanadate esters of glycerol and propane-1,3-diol , 1998 .

[23]  E. Tiekink,et al.  Intramolecular Electron Transfer in (BzImH)[(LOV)2O] (H2L = S-Methyl 3-((2-Hydroxyphenyl)methyl)dithiocarbazate): A Novel μ-Oxo Dinuclear Oxovanadium(IV/V) Compound with a Trapped-Valence (V2O3)3+ Core , 1997 .

[24]  C. R. Cornman,et al.  Oxidation of a Vanadium(V)−Dithiolate Complex to a Vanadium(V)−η2,η2-Disulfenate Complex , 1997 .

[25]  M. Zhou,et al.  Crystal structure of bovine low molecular weight phosphotyrosyl phosphatase complexed with the transition state analog vanadate. , 1997, Biochemistry.

[26]  Y. Deligiannakis,et al.  Models of Oxovanadium(IV)–Protein Interactions: The First Oxovanadium(IV) Complexes with Dipeptides , 1996 .

[27]  C. Rao,et al.  Monooxovanadium(V) mixed ligand complexes of schiff bases and catecholates : Synthesis, spectral and electrochemical characterization , 1996 .

[28]  A. Terzis,et al.  Model Investigations for Vanadium-Protein Interactions. Synthetic, Structural, and Physical Studies of Vanadium(III) and Oxovanadium(IV/V) Complexes with Amidate Ligands. , 1996, Inorganic chemistry.

[29]  K. K. Nanda,et al.  The First Oxovanadium(V)−Thiolate Complex, [VO(SCH2CH2)3N] , 1996 .

[30]  C. Rao,et al.  STRUCTURE, CHARACTERIZATION AND PHOTOREACTIVITY OF MONOMERIC DIOXOVANADIUM(V) SCHIFF-BASE COMPLEXES OF TRIGONAL-BIPYRAMIDAL GEOMETRY , 1996 .

[31]  S. P. Rath,et al.  Chemistry of oxovanadium(V) alkoxides: synthesis and structure of mononuclear complexes incorporating ethane-1,2-diol , 1996 .

[32]  M. Battell,et al.  Vanadium compounds as insulin mimics. , 1999, Metal ions in biological systems.

[33]  Alavattam Sreedhara,et al.  Oxovanadium(V) schiff base complexes of trishydroxymethylaminomethane with salicylaldehyde and its derivatives: Synthesis, characterization and redox reactivity , 1995 .

[34]  V. Pecoraro,et al.  Preparation of VO3+ and VO2 + complexes using hydrolytically stable, asymmetric ligands derived from Schiff base precursors , 1994 .

[35]  G. J. Leigh,et al.  Dalton perspectives. Metals in the nitrogenases , 1994 .

[36]  C. Carrano,et al.  Steric control of vanadium(V) coordination geometry: a mononuclear structural model for transition-state-analog RNase inhibitors , 1993 .

[37]  D. Rehder,et al.  Reactivity studies of mononuclear and dinuclear vanadium-sulfide-thiolate compounds , 1993 .

[38]  S. Gopinathan,et al.  Reactivity of bis(acetylacetonato)dinitrosylmolybdenum(0) towards schiff bases derived from salicylaldehyde or o-vanillin and benzoylhydrazide, or isonicotinoylhydrazide , 1993 .

[39]  C. R. Cornman,et al.  Implications for the Spectroscopic Assignment of Vanadium Biomolecules: Structural and Spectroscopic Characterization of Monooxovanadium(V) Complexes Containing Catecholate and Hydroximate Based Noninnocent Ligands , 1992 .

[40]  D. Crans,et al.  Nonreductive interaction of vanadate with an enzyme containing a thiol group in the active site: glycerol-3-phosphate dehydrogenase. , 1991, Biochemistry.

[41]  O. Howarth.  Vanadium-51 NMR , 1990 .

[42]  C. Carrano,et al.  Monomeric and dimeric vanadium(IV) and -(V) complexes of N-(hydroxyalkyl)salicylideneamines: structures, magnetochemistry and reactivity , 1990 .

[43]  H. Degani,et al.  Vanadium in Biological Systems , 1990, Springer Netherlands.

[44]  V. Pecoraro,et al.  Vanadium complexes of the tridentate Schiff base ligand N-salicylidene-N'-(2-hydroxyethyl)ethylenediamine: acid-base and redox conversion between vanadium(IV) and vanadium(V) imino phenolates , 1988 .

[45]  D. Rehder,et al.  Vanadium-51 shielding in vanadium(V) complexes: a reference scale for vanadium binding sites in biomolecules , 1988 .

[46]  M. Martínez-Maldonado,et al.  Mechanism of inhibition of glycolysis by vanadate. , 1987, Advances in experimental medicine and biology.

[47]  J. Nriagu,et al.  Cadmium in the Environment. Part 2. Health Effects. , 1983 .

[48]  C. Floriani,et al.  Chemistry and structure of an inorganic analog of a carboxylic acid: hydroxobis(8-quinolinato)oxovanadium(V) , 1982 .

[49]  H. Degani,et al.  Electron paramagnetic resonance studies and insulin-like effects of vanadium in rat adipocytes. , 1981, Biochemistry.

[50]  J. Bouchard,et al.  Peroxo complexes of molybdenum and tungsten stabilized by oxides of amines, phosphines, and arsines. Stability studies , 1980 .

[51]  M. Yates.  Biochemistry of Nitrogen Fixation , 1980 .

[52]  M. Ali,et al.  Metal complexes of sulphur and nitrogen-containing ligands: Complexes of s-benzyldithiocarbazate and a schiff base formed by its condensation with pyridine-2-carboxaldehyde , 1977 .

[53]  S. Livingstone,et al.  Metal chelates of dithiocarbazic acid and its derivatives. IX. Metal chelates of ten new schiff bases derived from S-methyldithiocarbazate , 1976 .