The 2-phosphaethynolate anion: convenient synthesis and the reactivity

Abstract

New members in the family of organophosphorus compounds: convenient synthesis and reactivity of the 2-phosphaethynolate anion are highlighted.

Isolation of Au-, Co-η1PCO and Cu-η2PCO complexes, conversion of an Ir–η1PCO complex into a dimetalladiphosphene, and an interaction-free PCO anion

“…Despite their early synthesis in 1992 by Becker, Westerhausen et al , 1 the reactivity of phosphaethynolate salts M + (PCO) – remained unexplored until the recent development of simple syntheses which allow for the preparation of large quantities of pure material. 2 These salts have been shown to undergo a variety of chemical transformations with organic substrates, 3 including cycloaddition reactions leading to phosphorus containing heterocycles. 4 In contrast, the strong reducing ability of PCO – salts 5 has hindered their exploration in transition metal chemistry.…”

Formation of a Uranium-Bound η1-Cyaphide (CP–) Ligand via Activation and C–O Bond Cleavage of Phosphaethynolate (OCP–)

“…Research interest in the long-sought and highly reactive cyaphide anion (CP – ), the phosphorus-containing analogue of the well-explored cyanide (CN – ) anion, has been ongoing for over a decade . Several cyaphide-containing compounds have been synthesized, including a range of phosphaalkynes and metal complexes with bridging cyaphide anions. − Reports of terminally bound, metal-coordinated cyaphide anions, however, are scarce and remain limited to two crystallographically characterized examples. The first example, namely [(dppe) 2 Ru­(H)­(CP)], featuring a terminal M–CP moiety, emerged in 2006 and was reported by Grützmacher and co-workers, followed by closely related examples reported by Crossley and co-workers in 2014, the cyaphide-alkynyl complexes [(dppe) 2 Ru­(CCR)­(CP)] (R = CO 2 Me, C 6 H 4 OMe) .…”

Synthesis and reactivity of a dialkyl‐2H‐1,2‐phosphasiliren‐3‐olate

“…NaOCP is well known as the "P" source reagent and is utilized in the synthesis of organophosphorus compounds (Scheme 1). [11] 2 is further purified by recrystallization from a cooled hexane solution to offer the pure material, in which 2 also shows excellent stability in both solid and solution state and can be stored at ambient temperatures for few months without decomposition in the glovebox. The experimental details are provided in the Electronic Supplementary Information (ESI).…”