Premium
Photoreactivity and Photopolymerization of Silicon‐Bridged [1]Ferrocenophanes in the Presence of Terpyridine Initiators: Unprecedented Cleavage of Both Iron–Cyclopentadienyl Bonds in the Presence of Chlorosilanes
Author(s) -
Chan Wing Yan,
Lough Alan J.,
Manners Ian
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700420
Subject(s) - chemistry , terpyridine , cyclopentadienyl complex , bond cleavage , reactivity (psychology) , cleavage (geology) , photopolymer , polymer chemistry , stoichiometry , yield (engineering) , silane , ligand (biochemistry) , metal , photochemistry , medicinal chemistry , polymerization , catalysis , organic chemistry , materials science , medicine , alternative medicine , polymer , pathology , fracture (geology) , metallurgy , biochemistry , receptor , composite material
Abstract The photopolymerisation of sila[1]ferrocenophane [Fe(η‐C 5 H 4 ) 2 SiMe 2 ] ( 3 ) with 4,4′,4′′‐tri‐ tert ‐butyl‐2,2′:6′,2′′‐terpyridine ( t Bu 3 terpy) as initiator has been explored. High‐molecular‐weight polyferrocenylsilane (PFS) [{Fe(η‐C 5 H 4 ) 2 SiMe 2 } n ] ( 5 ) was formed in high yield when a stoichiometric amount of t Bu 3 terpy was used at 5 °C. Photopolymerisation of ferrocenophane 3 at higher temperatures gave PFS 5 in lower yield and with a reduced molecular weight as a result of a slower propagation rate. Remarkably, when Me 3 SiCl was added as a capping agent before photopolymerisation, subsequent photolysis of the reaction mixture resulted in the unprecedented cleavage of both iron–Cp bonds in ferrocenophane 3 : iron(II) complex [Fe( t Bu 3 terpy) 2 Cl 2 ] ( 7 Cl ) was formed and the silane fragment (C 5 H 4 SiMe 3 ) 2 SiMe 2 ( 8 ) was released. The iron–Cp bond cleavage reaction also proceeded in ambient light, although longer reaction times were required. In addition, the unexpected cleavage chemistry in the presence of Me 3 SiCl was found to be applicable to other photoactive ferrocenes such as benzoylferrocene. For benzoylferrocene and ferrocenophane 3 , the presence of metal‐to‐ligand charge transfer (MLCT) character in their low‐energy transitions in the visible region probably facilitates photolytic iron–Cp bond cleavage, but this reactivity is suppressed when the strength of the iron–Cp bond is increased by the presence of electron‐donating substituents on the cyclopentadienyl rings.