Riesinger, Christoph and Balazs, Gabor and Seidl, Michael and Scheer, Manfred (2021) Substituted aromatic pentaphosphole ligands - a journey across the p-block. CHEMICAL SCIENCE, 12 (39). pp. 13037-13044. ISSN 2041-6520, 2041-6539
Full text not available from this repository. (Request a copy)Abstract
The functionalization of pentaphosphaferrocene [Cp*Fe(eta(5)-P-5)] (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){mu,eta(5:5)-(P-5)(2)EX2}][TEF] (EX2 = BBr2 (2), GaI2 (3), [TEF](-) = [Al{OC(CF3)(3)}(4)](-)) or mononuclear [Cp*Fe(eta(5)-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-P-5)(2)R) 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(mu, eta(5:2)-P-5)SbICp000][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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | INDEPENDENT CHEMICAL-SHIFTS; METAL-MEDIATED ACTIVATION; BOND COVALENT RADII; BASIS-SETS; PENTAPHOSPHACYCLOPENTADIENIDE ION; COORDINATION SPHERE; WHITE PHOSPHORUS; COMPLEXES; PENTAPHOSPHAFERROCENE; CHEMISTRY |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 07 Jul 2022 05:16 |
| Last Modified: | 07 Jul 2022 05:16 |
| URI: | https://pred.uni-regensburg.de/id/eprint/45825 |
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