Piesch, Martin and Seidl, Michael and Scheer, Manfred (2020) Transformations of thecyclo-P(4)ligand in [Cp ''' Co(eta(4)-P-4)]. CHEMICAL SCIENCE, 11 (26). pp. 6745-6751. ISSN 2041-6520, 2041-6539
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The reactivity of thecyclo-P(4)ligand complex [Cp ''' Co(eta(4)-P-4)] (1) (Cp ''' = 1,2,4-tri-tert-butyl-cyclopentadienyl) towards reduction and main group nucleophiles was investigated. By using K[CpFe(CO)(2)], a selective reduction to the dianionic complex [(Cp ''' Co)(2)(mu,eta(3):eta(3)-P-8)](2-)(2) was achieved. The reaction of1with(t)BuLi and LiCH(2)SiMe(3)as carbon-based nucleophiles yielded [Cp ''' Co(eta(3)-P4R)](-)(R =Bu-t (4), CH2SiMe3(7)), which, depending on the reaction conditions, undergo subsequent reactions with another equivalent of1to form [(Cp ''' Co)(2)(mu,eta(3):eta(3)-P8R)](-)(R =Bu-t (5), CH2SiMe3(8)). In the case of4, a different pathway was observed, namely a dimerisation followed by a fragmentation into [Cp ''' Co(eta(3)-(P5Bu2)-Bu-t)](-)(6) and [Cp ''' Co(eta(3)-P-3)](-)(3). With OH(-)as an oxygen-based nucleophile, the synthesis of [Cp ''' Co(eta(3)-P-4(O)H)](-)(9) was achieved. All compounds were characterized by X-ray crystal structure analysis, NMR spectroscopy and mass spectrometry. Their electronic structures and reaction behavior were elucidated by DFT calculations.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | BOND COVALENT RADII; MOLECULAR-STRUCTURE; WHITE PHOSPHORUS; COMPLEXES; LIGAND; P-4; FUNCTIONALIZATION; REACTIVITY; ACTIVATION; CRYSTAL; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 18 Mar 2021 08:53 |
| Last Modified: | 18 Mar 2021 08:53 |
| URI: | https://pred.uni-regensburg.de/id/eprint/44210 |
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