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Trinuclear Homo‐ and Heterometallic Complexes of a Doubly Bridged Cyclopentadienyl Ligand
Author(s) -
Siemeling Ulrich,
Jutzi Peter
Publication year - 1992
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19921250106
Subject(s) - chemistry , cyclopentadienyl complex , ferrocene , cyclopentadiene , decarbonylation , ligand (biochemistry) , valence (chemistry) , chloride , metal , medicinal chemistry , polymer chemistry , crystallography , inorganic chemistry , stereochemistry , catalysis , electrochemistry , organic chemistry , biochemistry , receptor , electrode
Metal complexes that are derived from the doubly bridged cyclopentadiene system 2,2,8,8‐tetramethyl‐2,8‐disilatricyclo[7.3.0.0 3,7 ] dodeca‐3,5,9,11‐tetraene (LH 2 ) are investigated. The dilithio salt of this compound (LLi 2 ) reacts with (Me 3 Si) 3 ‐C 5 H 2 FeCl to give, amongst other products, the trinuclear ferrocene [(Me 3 Si) 3 C 5 H 2 FeL] 2 Fe ( 2 ). A starting material well suited for the selective preparation of similar trinuclear complexes is the mononuclear ferrocene (HL 2 )Fe ( 3 ) which is formed by reaction of HLLi with iron(II) chloride. Reaction of dilithiiated 3 with trimethyltin chloride yields (Me 3 SnL) 2 Fe ( 4 ). Cocomplexation of dilithiated 3 and Cp*Li (Cp*=C 5 Me 5 ) with iron(II) chloride leads to the trinuclear ferrocene (Cp*FeL) 2 Fe ( 5 ). By reaction of 3 with octacarbonyldicobalt the heterometallic complex [(CO) 2 CoL] 2 Fe ( 6 ) is obtained, which yields [(CO)I 2 CoL] 2 Fe ( 7 ) by oxidative decarbonylation with iodine. The stereochemistry of the complexes presented is discussed. The trinuclear complexes 2 , 5 , 6 , and 7 are model systems for organometallic polymers with spatially directed structures, whose stability even in mixed‐valence states is evidenced by the mass spectra of these complexes.