NDLI: Metal-free and transition-metal tetraferrocenylporphyrins part 1: synthesis, characterization, electronic structure, and conformational flexibility of neutral compounds

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Subbotin, Roman I. Galloni, Pierluca Hadt, Ryan G. Nemykin, Victor N. Marrani, Andrea G. Loim, Nikolay M. Barrett, Christopher D. Zanoni, Robertino Floris, Barbara
Description	Author Affiliation: Nemykin VN ( Department of Chemistry & Biochemistry, University of Minnesota Duluth, Duluth, MN 55812, USA. vnemykin@d.umn.edu)
Abstract	$H_{2}TFcP$ [TFcP = 5,10,15,20-tetraferrocenyl porphyrin(2−)] was prepared by a direct tetramerization reaction between pyrrole and ferrocene carbaldehyde in the presence of a $BF_{3}catalyst,$ while the series of MTFcP (M = Zn, Ni, Co and Cu) were prepared by a metallation reaction between $H_{2}TFcP$ and respective metal acetates. All compounds were characterized by UV-vis and MCD spectroscopy , APCI MS and MS/MS methods, high-resolution ESI MS and XPS spectroscopy . Diamagnetic compounds were additionally characterized using $^{1}H$ and $^{13}C$ NMR methods, while the presence of low-spin iron(II) centers in the neutral compounds was confirmed by Mössbauer spectroscopy and by analysis of the XPS Fe 2p peaks, revealing equivalent Fe sites. XPS additionally showed the influence on Fe 2p binding energies exerted by the distinct central metal ions. The conformational flexibility of ferrocene substituents in $H_{2}TFcP$ and MTFcP, was confirmed using variable-temperature NMR and computational methods. Density functional theory predicts that α,β,α,β atropisomers with ruffled porphyrin cores represent minima on the potential energy surfaces of both $H_{2}TFcP$ and MTFcP. The degree of non-planarity is central-metal dependent and follows the trend: ZnTFcP < $H_{2}TFcP$ ∼ CuTFcP < CoTFcP < NiTFcP. In all cases, a set of occupied, predominantly ferrocene -based molecular orbitals were found between the highest occupied and the lowest unoccupied, predominantly porphyrin -based molecular orbitals. The vertical excitation energies of $H_{2}TFcP$ were calculated at the TDDFT level and confirm the presence of numerous predominantly metal-to- ligand charge-transfer bands coupled via configurational interaction with expected intra- ligand π–π* transitions.
ISSN	14779226
Journal	Dalton Trans.
Issue Number	32
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2008-08-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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