Hoidn, Christian M. and Maier, Thomas M. and Trabitsch, Karolina and Weigand, Jan J. and Wolf, Robert (2019) [3+2] Fragmentation of a Pentaphosphido Ligand by Cyanide. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 58 (52). pp. 18931-18936. ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
The activation of white phosphorus (P-4) by transition-metal complexes has been studied for several decades, but the functionalization and release of the resulting (organo)phosphorus ligands has rarely been achieved. Herein we describe the formation of rare diphosphan-1-ide anions from a P-5 ligand by treatment with cyanide. Cobalt diorganopentaphosphido complexes have been synthesized by a stepwise reaction sequence involving a low-valent diimine cobalt complex, white phosphorus, and diorganochlorophosphanes. The reactions of the complexes with tetraalkylammonium or potassium cyanide afford a cyclotriphosphido cobaltate anion 5 and 1-cyanodiphosphan-1-ide anions [R2PPCN](-) (6-R). The molecular structure of a related product 7 suggests a novel reaction mechanism, where coordination of the cyanide anion to the cobalt center induces a ligand rearrangement. This is followed by nucleophilic attack of a second cyanide anion at a phosphorus atom and release of the P-2 fragment.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | WHITE PHOSPHORUS; P-4 ACTIVATION; CYANOPHOSPHORUS COMPOUNDS; COMPLEXES; METAL; FUNCTIONALIZATION; TRANSFORMATION; TRIPHOSPHORUS; ALKYL; cobalt; cyanides; phosphorus; pnictides; redox-active ligands |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf |
| Depositing User: | Petra Gürster |
| Date Deposited: | 07 Apr 2020 07:58 |
| Last Modified: | 07 Apr 2020 07:58 |
| URI: | https://pred.uni-regensburg.de/id/eprint/25851 |
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