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Di‐ and Tetranuclear Dawson‐Derived Sandwich Complexes: Synthesis, Spectroscopic Characterization, and Electrochemical Behavior
Author(s) -
Ruhlmann Laurent,
Nadjo Louis,
Canny Jacqueline,
Contant Roland,
Thouvenot René
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(200203)2002:4<975::aid-ejic975>3.0.co;2-2
Subject(s) - chemistry , electrochemistry , characterization (materials science) , nanotechnology , polymer chemistry , combinatorial chemistry , inorganic chemistry , electrode , materials science
The reaction of α‐[P 2 W 15 O 56 ] 12− with divalent cations M 2+ leads to sandwich complexes of the formula [M 4 (H 2 O) 2 (P 2 W 15 O 56 ) 2 ] 16− (M 4 P 4 W 30 ) where M = Mn II , Co II , Ni II , Cu II , Zn II , or Cd II . An Fe III tetranuclear sandwich complex has also been obtained. Full details are reported concerning procedures by which the pure sandwich complexes can be obtained in good yield. A pure dinuclear trivalent Dawson‐derived sandwich complex of the formula [(H 2 O) 2 Na 2 Fe III 2 (P 2 W 15 O 56 ) 2 ] 16− has also been prepared as a water‐soluble sodium salt. All the compounds have been characterized by IR spectroscopy, elemental analysis, and 31 P NMR spectrometry. The acid‐base equilibria of the M 4 P 4 W 30 series have been studied. The electrochemical behavior of this series of sandwich complexes in aqueous solution has been investigated and systematic comparisons have been made. All these compounds exhibit successive reduction processes of the W atoms in a negative potential range, but in some cases the electrochemistry also involves redox reactions originating from the substituent transition metal (M), such as the reduction of Fe III and Cu II and the oxidation of Mn II . (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)