Moussa, Mehdi Elsayed and Kahoun, Tobias and Marquardt, Christian and Ackermann, Matthias T. and Hegen, Oliver and Seidl, Michael and Timoshkin, Alexey Y. and Virovets, Alexander V. and Bodensteiner, Michael and Scheer, Manfred (2023) Three- and Five-Membered Anionic Chains of Pnictogenylboranes. CHEMISTRY-A EUROPEAN JOURNAL, 29 (17): e202203206. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
An unprecedented family of three- and five-membered substituted anionic derivatives of parent pnictogenylboranes is herein reported. Reacting various combinations of the pnictogenylboranes H2E '-BH2-NMe3 (E '=P, As) with pnictogen-based nucleophiles MER1R2 (E=P, As; R1=H, R2=Bu-t; R1=R2=Ph; M=Na, K) allows for the isolation of the unsymmetrical products [Na(18-crown-6)][H2E '-BH2-(EHBu)-Bu-t] (3: E=E '=P; 4: E=E '=As; 5: E=As, E '=P) and [M(C)][H2E '-BH2-EPh2] (7: E=E '=P, M=Na, C=18-crown-6; 8: E=E '=As; M=K, C=[2.2.2]cryptand; 9: E=P, E '=As, M=Na, C=[2.2.2]cryptand; 10: E=As, E '=P, M=K, C=[2.2.2]cryptand). [Na(18-crown-6)][H2As-BH2-(BuPH)-Bu-t-BH3] (6) is only accessible by a different pathway, using (BuPH2)-Bu-t, BH3 . SMe2 and NaNH2 as starting materials. Additionally, the synthesis of symmetrical diphenyl-substituted compounds [M(18-crown-6)][Ph2E-BH2-EPh2] (11: E=P, M=Na; 12: E=As, M=K) is reported which can be regarded as isostructural inorganic, negatively charged analogs of dppm (1,1-bis(diphenylphosphino)methane) and dpam (1,1-bis(diphenylarsino)methane). Furthermore, an elongation of the pnictogen boron backbone in compounds 3, 7 and 9 ' (similar compound to 9, stabilized however by 18-crown-6), is attainable by reacting them with the pnictogenylboranes H2E '-BH2-NMe3 leading to corresponding five-membered chain-like compounds [Na(18-crown-6)][H2E-BH2-R1R2P-BH2-E ' H-2] (E=E '=P, R1=H, R2=Bu-t (13); E=E '=P, R1=R2=Ph (14); E=E '=As, R1=R2=Ph (15); E=P, E '=As, R1=R2=Ph (16)). Finally, the thermodynamics of the reaction pathways were evaluated by quantum chemical computations.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | PHOSPHINE-BORANE ADDUCTS; FRUSTRATED LEWIS PAIRS; HYDROPHOSPHINATION; PHOSPHINOBORANES; ROUTE; DEHYDROPOLYMERISATION; POLYMERIZATION; REDUCTION; MECHANISM; CO2; anionic chains; arsenic; boron; NMR spectroscopy; phosphorus |
| 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: | 10 Mar 2024 09:43 |
| Last Modified: | 10 Mar 2024 09:43 |
| URI: | https://pred.uni-regensburg.de/id/eprint/59521 |
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