Acyl-Phosphide Anions via an Intermediate with Carbene Character: Reactions of K[PtBu2] and CO.

Title Acyl-Phosphide Anions via an Intermediate with Carbene Character: Reactions of K[PtBu2] and CO.
Authors Xu, M.; Jupp, A.R.; Stephan, D.W.
Journal Angew Chem Int Ed Engl
DOI 10.1002/anie.201814562
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)][PtBu2 ] (1) with CO affords [(18-crown-6)K⋅THF2 ][Z-tBuP=C(tBu)O] (2⋅THF2 ) as the major product, and the minor product [K6 (18-crown-6)][(tBu2 PCO)2 ]3 (3). Species 2 reacts with either BPh3 or additional CO to give [K(18-crown-6)][(Ph3 B)tBuPC(tBu)O] (4) and [K(18-crown-6)][(OCtBu)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
Citation Xu, M.; Jupp, A.R.; Stephan, D.W..Acyl-Phosphide Anions via an Intermediate with Carbene Character: Reactions of K[PtBu2] and CO..

Related Elements

Phosphorus

15 P 30.973762000 Phosphorus

Phosphorus Bohr ModelSee more Phosphorus products. Phosphorus (atomic symbol: P, atomic number: 15) is a Block P, Group 15, Period 3 element. The number of electrons in each of Phosphorus's shells is 2, 8, 5 and its electronic configuration is [Ne] 3s2 3p3. The phosphorus atom has a radius of 110.5.pm and its Van der Waals radius is 180.pm. Phosphorus is a highly-reactive non-metallic element (sometimes considered a metalloid) with two primary allotropes, white phosphorus and red phosphorus its black flaky appearance is similar to graphitic carbon. Compound forms of phosphorus include phosphates and phosphides. Phosphorous was first recognized as an element by Hennig Brand in 1669 its name (phosphorus mirabilis, or "bearer of light") was inspired from the brilliant glow emitted by its distillation.

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