Maedl, Eric and Balazs, Gabor and Peresypkina, Eugenia V. and Scheer, Manfred (2016) Unexpected Reactivity of [(eta(5)-1,2,4-tBu(3)C(5)H(2))Ni(eta(3)-P-3)] towards Main Group Nucleophiles and by Reduction. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 55 (27). pp. 7702-7707. ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
The reduction of [Cp'''Ni(eta(3)-P-3)](1; Cp''' = eta(5)-1,2,4-tBu(3)C(5)H(2)) with potassium produces the complex anion [(Cp'''Ni)(2)(mu,eta(2:2)-P-8)](2-) (2), which contains a realgar-like P-8 unit. The anionic triple-decker sandwich complex [(Cp'''Ni)(2)(mu,eta(3:3)-P-3)](-) (3) with a cyclo-P-3 middle deck is obtained when 1 is treated with NaNH2 as a nucleophile. Na[3] can subsequently be oxidized with AgOTf to the neutral triple-decker complex [(Cp'''Ni)(2)(mu,eta(3:3)-P-3)] (4). In contrast, 1 reacts with LiPPh2 to give the anionic compound [(Cp'''Ni)(2)(mu,eta(2:2)-P6PPh2)](-) (5), a complex containing a bicyclic P-7 fragment capped by two Cp'''Ni units. Protonation of Li[5] with HBF4 leads to the neutral complex [(Cp'''Ni)(2)(mu,eta(2:2)-HP6PPh2)] (6). Adding LiNMe2 to 1 results in [Cp'''Ni(eta(2)-P3NMe2)](-) (7) becoming accessible, a complex which forms as a result of nucleophilic attack at the cyclo-P3 ring of 1. The complexes K-2[2], Na[3], 4, 6, and Li[7] were fully characterized and their structures determined by single-crystal X-ray diffraction. The stoichiometric and catalytic reactivity of organometallic
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | TRANSITION-METAL-COMPLEXES; COORDINATION CHEMISTRY; CYCLO-TRIPHOSPHORUS; P-4 ACTIVATION; PHOSPHORUS; LIGANDS; PENTAPHOSPHAFERROCENE; FERROCENE; ANIONS; STABILIZATION; electrophilic reactivity; nickel; phosphorus; reduction chemistry; triple decker complexes |
| 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: | 15 Mar 2019 11:22 |
| Last Modified: | 15 Mar 2019 11:22 |
| URI: | https://pred.uni-regensburg.de/id/eprint/3746 |
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