Solution equilibria and redox properties of schiff base complexes of oxomolybdenum (V) in dimethylformamide solution

Bradbury, Julie R., Hanson, Graeme R., Bond, Alan M. and Wedd, Anthony G. (1984) Solution equilibria and redox properties of schiff base complexes of oxomolybdenum (V) in dimethylformamide solution. Inorganic Chemistry, 23 7: 844-848. doi:10.1021/ic00175a010


Author Bradbury, Julie R.
Hanson, Graeme R.
Bond, Alan M.
Wedd, Anthony G.
Title Solution equilibria and redox properties of schiff base complexes of oxomolybdenum (V) in dimethylformamide solution
Journal name Inorganic Chemistry   Check publisher's open access policy
ISSN 0020-1669
Publication date 1984-03
Sub-type Article (original research)
DOI 10.1021/ic00175a010
Volume 23
Issue 7
Start page 844
End page 848
Total pages 5
Place of publication Easton, PA. U.S.A.
Publisher American Chemical Society
Language eng
Subject 030201 Bioinorganic Chemistry
Formatted abstract
Measurement of spin and free halide concentrations in solutions of trans-[MoOL(MeOH)]Br (H2L = H2SALOPHEN, H2SALPN, H2SALEN) and [MoO(SALPN)Cl] in DMF (1-5 mM Mo; 0.1 M Et4NX; X = PF6, Cl, Br) indicates the presence of equilibria between mononuclear and polynuclear species. For [MoO(SALOPHEN)(MeOH)]Br in the presence of 0.1 M PF6-, the mononuclear cation trans- [MoO(SALOPHEN)(DMF)]+ is present at a concentration of about 100 mol % but equivalent solutions of [MoOL(MeOH)]Br (H2L = H2SALPN, H2SALEN) contain low concentrations (ca. 10 mol %) of ESR-silent polynuclear species containing bound bromide. For [MoO(SALPN)Cl] solutions, the concentration of polynuclear species is much higher, being >50 mol % Mo in PF6- media and >85 mol% in Cl- media. The dominant mononuclear species appears to be [MoO(SALPN)Cl]. The electrochemistry of these systems is complicated by the equilibria and an unequivocal interpretation is not possible from the present (quite extensive) data. Examination of the first reduction process for each system suggests that the halide-bound complexes are electroactive, even for [MoO(SALOPHEN)(MeOH)]Br in 0.1 M PF6- media where the free bromide concentration is about 100 mol %. For [MoO(SALPN)Cl], reduction of both mononuclear and polynuclear species is observed. The total data appear to reflect the tendency of mononuclear oxomolybdenum(V) species (4d1) to associate in solution to form binuclear or polynuclear products that are stabilized by spin-spin interactions, whereas the oxomolybdenum(IV) analogues tend to thermodynamically favor mononuclear (low-spin d2) forms. © 1984 American Chemical Society.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Centre for Advanced Imaging Publications
 
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