3, 4‐Ferrocenyl‐Functionalized Pyrroles: Synthesis, Structure, and (Spectro)Electrochemical Studies. Issue 6 (15th January 2014)

• Record Type: Journal Article
• Authors: Korb, Marcus; Pfaff, Ulrike; Hildebrandt, Alexander; Rüffer, Tobias; Lang, Heinrich
• Is Part Of: European journal of inorganic chemistry. Issue 6(2014)
• Page Start: 1051
• Page End: 1061
• Publication Date: 2014-01-15
• Subjects: Metallocenes -- Alkynes -- Heterocycles -- Electrochemistry -- Electron transfer; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201301423
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The synthesis of 3, 4‐diferrocenyl‐substituted pyrroles of the type 3, 4‐Fc2 ‐ c C4 H2 NR [Fc = Fe(η 5 ‐C5 H4 )(η 5 ‐C5 H5 ); R = Ph (3a ), SO2 ‐4‐MeC6 H4 (Ts) (3b ), Si i Pr3 (3c )], 3, 4‐(FcC≡C)2 ‐ c C4 H2 NR [R = Ph (4a ), Ts (4b )], and 3‐Br‐4‐FcC≡C‐ c C4 H2 NR [R = Ph (7a ), Ts (7b )] from 3, 4‐Br2 ‐ c C4 H2 NR [R = Ph (2a ), Ts (2b ), Si i Pr3 (2c )] is discussed. The molecular structures of3a, b, 5, 4b, and7b in the solid state are reported and show that the formal double bonds in the heterocyclic core are rather localized relative to pyrrole itself. The investigations with (spectro)electrochemical methods reveal the different capabilities for the formation of mixed‐valent species and allows the classification of3a, b as class II systems, whereas compounds that feature electron‐withdrawing –C≡C– units (4a, b ) can be assigned to class I systems according to Robin and Day. Abstract : The synthesis and solid‐state structures of 3, 4‐diferrocenyl‐substituted pyrroles are reported. (Spectro)electrochemical investigations allow the classification of these compounds as class II (NPh, NTs) or as class I systems for compounds including an additional –C≡C– unit between the ferrocenyl groups and the heterocyclic core.