Acyl‐Phosphide Anions via an Intermediate with Carbene Character: Reactions of K[PtBu2] and CO. (6th February 2019)

• Record Type: Journal Article
• Authors: Xu, Maotong; Jupp, Andrew R.; Stephan, Douglas W.
• Is Part Of: Angewandte Chemie. Volume 131:Number 11(2019)
• Page Start: 3586
• Page End: 3590
• Publication Date: 2019-02-06
• Subjects: Anionen -- Carbene -- Migrationen -- Kalium -- Strukturaufklärung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201814562
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The analogy of the reactivity of group 1 phosphides to that of FLPs is further demonstrated by reactions with CO, affording a new synthetic route to acyl‐phosphide anions. The reaction of [K(18‐crown‐6)][P t Bu2 ] (1 ) with CO affords [(18‐crown‐6)K⋅THF2 ][ Z ‐ t BuP=C( t Bu)O] (2⋅THF2 ) as the major product, and the minor product [K6 (18‐crown‐6)][( t Bu2 PCO)2 ]3 (3 ). Species 2 reacts with either BPh3 or additional CO to give [K(18‐crown‐6)][(Ph3 B) t BuPC( t Bu)O] (4 ) and [K(18‐crown‐6)][(OC t Bu)2 P] (5 ), respectively. The acyl‐phosphide anion 2 is thought to be formed by a photochemically induced radical process involving a transient species with triplet carbene character, prompting 1, 2‐ tert ‐butyl group migration. A similar process is proposed for the subsequent reaction of 2 with CO to give 5 . Abstract : Das Anion [P t Bu2 ] − reagiert mit CO zu einer kurzlebigen Zwischenstufe mit Carbencharakter. Diese Spezies geht entweder eine 1, 2‐Alkylmigration oder eine Dimerisierung zu Acylphosphid‐Anionen ein. In ähnlicher Weise reagiert eines dieser Anionen weiter mit CO zu einem Diacylphosphid‐Anion.