Indium‐Bridged [1]Ferrocenophanes. Issue 8 (24th January 2014)

• Record Type: Journal Article
• Authors: Bagh, Bidraha; Sadeh, Saeid; Green, Jennifer C.; Müller, Jens
• Is Part Of: Chemistry. Volume 20:Issue 8(2014)
• Page Start: 2318
• Page End: 2327
• Publication Date: 2014-01-24
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201303925
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Indium‐bridged [1]ferrocenophanes ([1]FCPs) and [1.1]ferrocenophanes ([1.1]FCPs) were synthesized from dilithioferrocene species and indium dichlorides. The reaction of Li<sub>2</sub>fc⋅tmeda (fc=(H<sub>4</sub>C<sub>5</sub>)<sub>2</sub>Fe) and (Mamx)InCl<sub>2</sub> (Mamx=6‐(Me<sub>2</sub>NCH<sub>2</sub>)‐2, 4‐<italic>t</italic>Bu<sub>2</sub>C<sub>6</sub>H<sub>2</sub>) gave a mixture of the [1]FCP (Mamx)Infc (<bold>4<sub>1</sub></bold>), the [1.1]FCP [(Mamx)Infc]<sub>2</sub> (<bold>4<sub>2</sub></bold>), and oligomers [(Mamx)Infc]<sub><italic>n</italic></sub> (<bold>4</bold><sub><italic><bold>n</bold></italic></sub>). In a similar reaction, employing the enantiomerically pure, planar‐chiral (<italic>S<sub>p</sub>, S<sub>p</sub></italic>)‐1, 1′‐dibromo‐2, 2′‐diisopropylferrocene (<bold>1</bold>) as a precursor for the dilithioferrocene derivative Li<sub>2</sub>fc<sup><italic>i</italic>Pr2</sup>, equipped with two <italic>i</italic>Pr groups in the α position, gave the inda[1]ferrocenophane <bold>5<sub>1</sub></bold> [(Mamx)Infc<sup><italic>i</italic>Pr2</sup>] selectively. Species <bold>5<sub>1</sub></bold> underwent ring‐opening polymerization to give the polymer <bold>5</bold><sub><italic><bold>n</bold></italic></sub>. The reaction between Li<sub>2</sub>fc<sup><italic>i</italic>Pr2</sup> and Ar′InCl<sub>2</sub> (Ar′=2‐(Me<sub>2</sub>NCH<sub>2</sub>)C<sub>6</sub>H<sub>4</sub>) gave an inseparable mixture of the [1]FCP Ar′Infc<sup><italic>i</italic>Pr2</sup> (<bold>6<sub>1</sub></bold>) and the [1.1]FCP [Ar′Infc<sup><italic>i</italic>Pr2</sup>]<sub>2</sub> (<bold>6<sub>2</sub></bold>). Hydrogenolysis reactions (BP86/TZ2P) of the four inda[1]ferrocenophanes revealed that the structurally most distorted species (<bold>5<sub>1</sub></bold>) is also the most strained [1]FCP.</p> </abstract>