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Unique Bora[1]ferrocenophanes with Sterically Protected Boron: A Potential Gateway to Helical Polyferrocenes
Author(s) -
Bhattacharjee Hridaynath,
Zhu Jianfeng,
Müller Jens
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201908993
Subject(s) - bathochromic shift , monomer , chemistry , boron , circular dichroism , crystallography , steric effects , polymerization , polymer , polymer chemistry , stereochemistry , organic chemistry , fluorescence , physics , quantum mechanics
Silicon‐bridged [1]ferrocenophanes are a versatile class of monomers to obtain well‐defined metallopolymers, however, their boron‐bridged analogues are far less utilized despite being significantly higher strained. We assumed that the reactivity of known bora[1]ferrocenophanes towards ring‐opening polymerization is hampered by π‐donating R 2 N groups at the bridging boron atom and therefore prepared the first bora[1]ferrocenophanes lacking such electronic stabilization. The new, isolated ferrocenophane with a 2,4,6‐triisopropylphenyl group attached to the bridging boron atom exhibits the most tilted Cp rings among all isolated strained sandwich compounds [α(DFT)=33.3°] with a measured record value of the bathochromic shift ( λ max =516 nm). Attempts to purify the mesityl analogue by vacuum sublimation transformed this monomer to a purple‐colored polymer that resulted in Cotton effects in circular dichroism spectroscopy. DFT calculations revealed a left‐handed helical structure for this polymer. This is the first evidence for a polyferrocene with a chiral secondary structure.