Substituted aromatic pentaphosphole ligands – a journey across the p-block

Abstract

The functionalization of pentaphosphaferrocene [Cp*Fe(η5-P5)] (1) with cationic group 13–17 electrophiles is shown to be a general synthetic strategy towards P–E bond formation of unprecedented diversity. The products of these reactions are dinuclear [{Cp*Fe}2{μ,η5:5-(P5)2EX2}][TEF] (EX2 = BBr2 (2), GaI2 (3), [TEF] = [Al{OC(CF3)3}4]) or mononuclear [Cp*Fe(η5-P5E)][X] (E = CH2Ph (4), CHPh2 (5), SiHPh2 (6), AsCy2 (7), SePh (9), TeMes (10), Cl (11), Br (12), I (13)) complexes of hetero-bis-pentaphosphole ((cyclo-P5)2R) or hetero-pentaphosphole ligands (cyclo-P5R), the aromatic all-phosphorus analogs of prototypical cyclopentadienes. Further, modifying the steric and electronic properties of the electrophile has a drastic impact on its reactivity and leads to the formation of [Cp*Fe(μ,η5:2-P5)SbICp′′′][TEF] (8) which possesses a triple-decker-like structure. X-ray crystallographic characterization reveals the slightly twisted conformation of the cyclo-P5R ligands in these compounds and multinuclear NMR spectroscopy confirms their integrity in solution. DFT calculations shed light on the bonding situation of these compounds and confirm the aromatic character of the pentaphosphole ligands on a journey across the p-block.

Graphical abstract: Substituted aromatic pentaphosphole ligands – a journey across the p-block

Supplementary files

Article information

Article type
Edge Article
Submitted
05 Aug 2021
Accepted
03 Sep 2021
First published
14 Sep 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021, Advance Article

Substituted aromatic pentaphosphole ligands – a journey across the p-block

C. Riesinger, G. Balázs, M. Seidl and M. Scheer, Chem. Sci., 2021, Advance Article , DOI: 10.1039/D1SC04296C

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