Indium-bridged [1]ferrocenophanes.
Indium-bridged [1]ferrocenophanes ([1]FCPs) and [1.1]ferrocenophanes ([1.1]FCPs) were synthesized from dilithioferrocene species and indium dichlorides. The reaction of Li2fc⋅tmeda (fc = (H4C5)2Fe) and (Mamx)InCl2 (Mamx = 6-(Me2NCH2)-2,4-tBu2C6H2) gave a mixture of the [1]FCP (Mamx)Infc (4(1)), the [1.1]FCP [(Mamx)Infc]2 (4(2)), and oligomers [(Mamx)Infc]n (4(n)). In a similar reaction, employing the enantiomerically pure, planar-chiral (Sp,Sp)-1,1'-dibromo-2,2'-diisopropylferrocene (1) as a precursor for the dilithioferrocene derivative Li2fc(iPr2), equipped with two iPr groups in the α position, gave the inda[1]ferrocenophane 5(1) [(Mamx)Infc(iPr2)] selectively. Species 5(1) underwent ring-opening polymerization to give the polymer 5(n). The reaction between Li2fc(iPr2) and Ar'InCl2 (Ar' = 2-(Me2NCH2)C6H4) gave an inseparable mixture of the [1]FCP Ar'Infc(iPr2) (6(1)) and the [1.1]FCP [Ar'Infc(iPr2)]2 (6(2)). Hydrogenolysis reactions (BP86/TZ2P) of the four inda[1]ferrocenophanes revealed that the structurally most distorted species (5(1)) is also the most strained [1]FCP.
Department of Chemistry, University of Saskatchewan, 110 Science Place, Saskatoon, Saskatchewan S7N 5C9 (Canada), Fax: (+1) 306-966-4730; Present address: Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6 (Canada).
Bidraha
B
Bagh
Saeid
S
Sadeh
Jennifer C
JC
Green
Jens
J
Müller
density functional calculations; ferrocenophanes; indium; metallocenes; ring-opening polymerization