Hauer, Sebastian and Horsley Downie, Thomas M. and Balazs, Gabor and Schwedtmann, Kai and Weigand, Jan J. and Wolf, Robert (2024) Cobalt-Mediated [3+1] Fragmentation of White Phosphorus: Access to Acylcyanophosphanides. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 63 (6). ISSN 1433-7851, 1521-3773
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Despite the accessibility of numerous transition metal polyphosphido complexes through transition-metal-mediated activation of white phosphorus, the targeted functionalization of P-n ligands to obtain functional monophosphorus species remains challenging. In this study, we introduce a new [3+1] fragmentation procedure for cyclo-P-4 ligands, leading to the discovery of acylcyanophosphanides and -phosphines. Treatment of the complex [K(18c-6)][(Ar*BIAN)Co(eta(4)-P-4)] ([K(18c-6)]3, 18c-6=[18]crown-6, Ar*=2,6-dibenzhydryl-4-isopropylphenyl, BIAN=1,2-bis(arylimino)acenaphthene diimine) with acyl chlorides results in the formation of acylated tetraphosphido complexes [(Ar*BIAN)Co(eta(4)-P4C(O)R)] (R=tBu, Cy, 1-Ad, Ph; 4 a-d). Subsequent reactions of 4 a-d with cyanide salts yield acylated cyanophosphanides [RC(O)PCN](-) (9 a-d(-)) and the cyclo-P-3 cobaltate anion [(Ar*BIAN)Co(eta(3)-P-3)(CN)](-) (8(-)). Further reactions of 4 a-d with trimethylsilyl cyanide (Me3SiCN) and isocyanides provide insight into a plausible mechanism of this [3+1] fragmentation reaction, as these reagents partially displace the P4C(O)R ligand from the cobalt center. Several potential intermediates of the [3+1] fragmentation were characterized. Additionally, the introduction of a second acyl substituent was achieved by treating [K(18c-6)]9b with CyC(O)Cl, resulting in the first bis(acyl)monocyanophosphine (CyC(O))(2)PCN (10).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | SELECTIVE P-4 ACTIVATION; BOND COVALENT RADII; OXIDE PHOTOINITIATORS; COORDINATION SPHERE; FUNCTIONALIZATION; COMPLEXES; REACTIVITY; TRANSFORMATION; ELEMENTS; LIGANDS; Cobalt; Cyanides; P-4 Activation; Phosphorus; Pnictides |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 16 Dec 2025 07:59 |
| Last Modified: | 16 Dec 2025 07:59 |
| URI: | https://pred.uni-regensburg.de/id/eprint/63883 |
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