1,1‘-Ferrocenyldicarboxylic Acid as Starting Material for the Formation of Trimetallic Ti(IV)−Fe(II)−Cu(I) and Pentametallic Ti₂(IV)−Fe(II)−Cu₂(I) Complexes

Abstract

Reaction of {[Ti](C⋮C t Bu) 2 }CuCH 3 ( 1 ) {[Ti] = (η 5 -C 5 H 4 SiMe 3 ) 2 Ti} with 1,1‘-(η 5 -C 5 H 4 CO 2 H) 2 Fe ( 2 ) results in the formation of either the heterotrinuclear complex {[Ti](C⋮C t Bu) 2 }CuO 2 C(η 5 -C 5 H 4 )Fe(η 5 -C 5 H 4 CO 2 H) ( 3 ) or the pentametallic complex [{[Ti](C⋮C t Bu) 2 }CuO 2 C(η 5 -C 5 H 4 )] 2 Fe ( 4 ), depending on the stoichiometric ratio of the reactants. Compound 4 can also be obtained by reacting 3 with 1 equiv of 1 . When 3 is reacted with a stoichiometric quantity of {[Ti](C⋮CSiMe 3 ) 2 }CuCH 3 ( 5 ), the asymmetric complex {[Ti](C⋮C t Bu) 2 }CuO 2 C(η 5 -C 5 H 4 )Fe(η 5 -C 5 H 4 )CO 2 Cu{(Me 3 SiC⋮C) 2 [Ti]} ( 6 ) is produced. While in 4 two identical {[Ti](C⋮C t Bu) 2 }Cu moieties are bridged by an [O 2 C(η 5 -C 5 H 4 )] 2 Fe entity, in 6 two different organometallic building blocks, such as {[Ti](C⋮C t Bu) 2 }Cu and {[Ti](C⋮CSiMe 3 ) 2 }Cu are linked by the same unit. The electrochemical behavior of complexes 3, 4, and 6 is discussed.