Premium
Vanadium(IV/V) Complexes Containing [VO] 2+ , [VO] 3+ , [VO 2 ] + and [VO(O 2 )] + Cores with Ligands Derived from 2‐Acetylpyridine and S ‐Benzyl‐ or S ‐Methyldithiocarbazate
Author(s) -
Maurya Mannar R.,
Khurana Shilpa,
Zhang Wenjian,
Rehder Dieter
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200207)2002:7<1749::aid-ejic1749>3.0.co;2-g
Subject(s) - chemistry , ligand (biochemistry) , vanadium , medicinal chemistry , denticity , methanol , trigonal bipyramidal molecular geometry , malonate , crystal structure , stereochemistry , inorganic chemistry , crystallography , organic chemistry , receptor , biochemistry
Vanadium complexes containing [VO] 2+ , [VO] 3+ , [VO 2 ] + and [VO(O 2 )] + 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 [VO 2 L] [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 H 2 O 2 , catechol or benzhydroxamic acid gave rise to oxo(peroxo)vanadium complexes [VO(O 2 )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 PPh 3 . 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)