Cationic polypnictogen complexes as building blocks for novel ferrocenes

Widmann M, Zhang Z, Rehse A, Balázs G, Timoshkin AY, Meyer K, Winter R, Scheer M (2026)

Publication Type: Journal article

Publication year: 2026

Journal

Inorganic Chemistry Frontiers Royal Society of Chemistry (RSC)

Book Volume: 13

Pages Range: 3112-3119

Journal Issue: 7

DOI: 10.1039/d5qi02477c

Abstract

The systematic nucleophilic functionalisation of the cationic pentaphosphole ligand complex [Cp*Fe(η⁴-P5Me)][OTf] ([OTf]⁻ = [SO3CF3]⁻) (A) with sterically demanding Cp^R derivatives is reported. This newly developed protocol turned out to be a highly reliable method for the synthesis of end-deck cyclo-P5 ligand complexes bearing bulky Cp^R substituents. By the reaction of A with anionic Cp^R salts, complexes of the type [Cp*Fe(η⁴-P5MeCp^R)] (Cp* = η⁵-C5Me5; Cp^R = Cp′ (1), Cp″ (2), Cp‴ (3), Cp^Me (4); Cp′ = η⁵-C5H4^tBu, Cp″ = η⁵-1,3-^tBu2C5H3, Cp‴ = η⁵-1,3,4-^tBu3C5H2, Cp^Me = η⁵-C5Me4H) are obtained. All products feature a selective 1,1′-disubstitution at the cyclo-P5 ligand. Further reactivity studies of these complexes with FeBr2 enabled the formation of novel, sterically demanding ferrocene derivatives [{Cp*Fe(η⁴-P5Me(η⁵-Cp″))}2Fe] (5) and [Cp*Fe(η⁴-P5Me(η⁵-Cp″))FeCp″] (6), featuring three different Fe atoms in a ferrocene-like environment. Oxidation of 5 yielded the dicationic complex [{Cp*Fe(η⁴-P5Me(η⁵-Cp″))}2Fe][FAl]2 (7). EPR, zero-field ⁵⁷Fe Mössbauer, as well as DFT investigations on 7 showed a symmetric distribution of the positive charges on the outer Fe atoms.

Authors with CRIS profile

Zihan Zhang Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Universität Konstanz

Germany (DE) Universität Regensburg

Germany (DE) Saint Petersburg State University (SPbU) / Санкт-Петербургский государственный университет (СПбГУ)

Russian Federation (RU)

How to cite

APA:

Widmann, M., Zhang, Z., Rehse, A., Balázs, G., Timoshkin, A.Y., Meyer, K.,... Scheer, M. (2026). Cationic polypnictogen complexes as building blocks for novel ferrocenes. Inorganic Chemistry Frontiers, 13(7), 3112-3119. https://doi.org/10.1039/d5qi02477c

MLA:

Widmann, Maximilian, et al. "Cationic polypnictogen complexes as building blocks for novel ferrocenes." Inorganic Chemistry Frontiers 13.7 (2026): 3112-3119.

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