Riesinger, Christoph and Balazs, Gabor and Bodensteiner, Michael and Scheer, Manfred (2020) Stabilization of Pentaphospholes as eta(5)-Coordinating Ligands. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 59 (52). pp. 23879-23884. ISSN 1433-7851, 1521-3773
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Electrophilic functionalisation of [Cp*Fe(eta(5)-P-5)] (1) yields the first transition-metal complexes of pentaphospholes (cyclo-P5R). Silylation of1with [(Et3Si)(2)(mu-H)][B(C6F5)(4)] leads to the ionic species [Cp*Fe(eta(5)-P5SiEt3)][B(C6F5)(4)] (2), whose subsequent reaction with H2O yields the parent compound [Cp*Fe(eta(5)-P5H)][B(C6F5)(4)] (3). The synthesis of a carbon-substituted derivative [Cp*Fe(eta(5)-P5Me)][X] ([X](-)=[FB(C6F5)(3)](-)(4 a), [B(C6F5)(4)](-)(4 b)) is achieved by methylation of1employing [Me3O][BF4] and B(C6F5)(3)or a combination of MeOTf and [Li(OEt2)(2)][B(C6F5)(4)]. The structural characterisation of these compounds reveals a slight envelope structure for the cyclo-P5R ligand. Detailed NMR-spectroscopic studies suggest a highly dynamic behaviour and thus a distinct lability for2and3in solution. DFT calculations shed light on the electronic structure and bonding situation of this unprecedented class of compounds.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | INDEPENDENT CHEMICAL-SHIFTS; HALF-SANDWICH COMPLEXES; TRIPLE-DECKER COMPLEXES; METALLOCENE CATALYSTS; BASIS-SETS; X-RAY; COVALENT RADII; PENTAPHOSPHAFERROCENE; AROMATICITY; PHOSPHORUS; electrophilic functionalisation; iron; pentaphosphole; polyphosphorus ligands; protonation |
| 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: | 08 Mar 2021 13:35 |
| Last Modified: | 08 Mar 2021 13:35 |
| URI: | https://pred.uni-regensburg.de/id/eprint/43530 |
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