Heinl, Veronika and Seidl, Michael and Balazs, Gabor and Scheer, Manfred (2023) Reactivity of [Cp′′₂/sub>Zr(η¹:¹-E₄)] (E=P, As) towards Nucleophiles. CHEMISTRY-A EUROPEAN JOURNAL, 29 (34): e202301016. ISSN 0947-6539, 1521-3765
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The functionalization of the polypnictogen ligand complexes [Cp '' Zr-2(eta(1:1)-E-4)] (E=P (1 a), As (1 b); Cp ''=1,3-di-tertbutyl-cyclopentadienyl) is focused to modify the features of the polypnictogen unit to explore new synthetic pathways for further transformations. The reaction behavior of 1 towards main group nucleophiles is investigated. The reaction of 1 a with (BuLi)-Bu-t leads to the ionic product Li[Cp '' Zr-2(eta(1:1)-(P4Bu)-Bu-t)] (2) where an organic group is attached to a bridgehead phosphorus atom of the butterfly unit. Further reactions of 2 with quenching electrophilic reagents enable the introduction of other substituents. Moreover, a condensation of 2 to [(Cp '' Zr-2)(2)(mu,eta(1:1:1:1)-(P8Bu2)-Bu-t)] (3), containing a novel P-8-unit, has been observed. The reaction of 1 with LiNMe2 and LiCH2SiMe3 leads to a partial fragmentation of the E-4 unit and the compounds [Cp '' Zr-2(eta(2)-E(3)Nu)] (Nu=NMe2: E=P (6 a), As (6 b); Nu=CH2SiMe3: E=P (7 a), As (7 b)) are formed.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | WHITE PHOSPHORUS; ELEMENTAL PHOSPHORUS; CRYSTAL-STRUCTURE; P-4 ACTIVATION; FUNCTIONALIZATION; ACID; BOND; PHOSPHINES; BEHAVIOR; RHODIUM; arsenic; nucleophile; phosphorus; polypnictogen complexes; triple decker complex |
| 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: | 28 Feb 2024 05:22 |
| Last Modified: | 28 Feb 2024 05:22 |
| URI: | https://pred.uni-regensburg.de/id/eprint/59103 |
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