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Preparation and Electrochemical Properties of Polynuclear Organometallic Complexes Derived from Ferrocene‐Containing Bidentate Ligands
Author(s) -
Horikoshi Ryo,
Mochida Tomoyuki,
Torigoe Reiko,
Yamamoto Yasuhiro
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(200212)2002:12<3197::aid-ejic3197>3.0.co;2-t
Subject(s) - chemistry , ferrocene , denticity , redox , metal , electrochemistry , stereochemistry , medicinal chemistry , metallocene , metal ions in aqueous solution , crystallography , rhodium , inorganic chemistry , catalysis , organic chemistry , electrode , polymerization , polymer
The reaction of the ferrocene‐containing bridging ligands 1,1′‐bis(4‐pyridylthio)ferrocene ( 1 ), 1′,1′′′‐bis(4‐pyridylthio)biferrocene ( 2 ), and 1′,1′′′‐bis(diphenylphosphanyl)biferrocene ( 3 ), with the chloro‐bridged dinuclear complexes [( p ‐cymene)RuCl(μ‐Cl)] 2 and [Cp*MCl(μ‐Cl)] 2 (M = Rh, Ir) affords trinuclear and tetranuclear metal complexes in good yields: [{( p ‐cymene)RuCl(μ‐Cl)} 2 (μ‐L)] ( 4 : L = 1 ; 7 : L = 2 ; 10 : L = 3 ), [{Cp*MCl(μ‐Cl)} 2 (μ‐L)] ( 5 : L = 1 , M = Rh; 6 : L = 1 , M = Ir, 8 : L = 2 , M = Rh; 9 : L = 2 , M = Ir; 11 : L = 3 , M = Rh; 12 : L = 3 , M = Ir). The molecular structures of 3 and 5 have been determined by X‐ray structure analysis. These complexes show quasi‐reversible redox processes of the bridging ligands as well as irreversible redox processes of the terminal metal ions. Reaction of [{Cp*MCl(μ‐Cl)} 2 (μ‐ 1 )] with AgPF 6 affords [{(Cp*M) 4 (μ‐Cl) 4 }(μ‐ 1 ) 2 ](PF 6 ) 4 ( 13 : M = Rh, 14 : M = Ir), which are chloro‐bridged polynuclear complexes.