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Unique Bora[1]ferrocenophanes with Sterically Protected Boron: A Potential Gateway to Helical Polyferrocenes
Authors:Hridaynath Bhattacharjee  Jianfeng Zhu  Jens Müller
Abstract: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 bora1]ferrocenophanes towards ring‐opening polymerization is hampered by π‐donating R2N groups at the bridging boron atom and therefore prepared the first bora1]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 (λmax=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.
Keywords:Boron  Chiralitä  t  Gespannte Molekü  le  Helikale Strukturen  Ringö  ffnende Polymerisation
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