Uranium and thorium complexes of the phosphaethynolate ion

Abstract

New tris-amidinate actinide (Th, U) complexes containing a rare O-bound terminal phosphaethynolate (OCP–) ligand were synthesized and fully characterized.

Trapping of a Highly Bent and Reduced Form of 2‐Phosphaethynolate in a Mixed‐Valence Diuranium–Triamidoamine Complex

“…Forexample,strongly reducing [U{N(OAr Ad,Me ) 3 }(DME)] [N(OAr Ad,Me ) 3 = trianion of tris(2hydroxy-3-(1-adamantyl)-5-methylbenzyl)amine] cleaves the CÀObond of OCP À to give an oxo-bridged dinuclear product containing cyaphide,CP À , [6] whereas the more weakly reducing [Ti(OCP){HC(CMeNAr) 2 }(OAr)] (Ar = 2,6-diisopropylphenyl) cleaves the C À Pb ond to release CO and give aP 2 derivative. [8] Notably,i nt he unique case of [Th{m-h 1 (O):h 2 (PC)-OCP-Ni(COD)}{PhC(NSiMe 3 ) 2 } 3 ]( I), [9] theP -C-O angle is 148.1-(3)8 8.T his suggests ar educed form of OCP À by Ni!PC backbonding,b ut the extent of OCP À reduction remains an open question since instability of this complex hampered its characterisation. [8] Notably,i nt he unique case of [Th{m-h 1 (O):h 2 (PC)-OCP-Ni(COD)}{PhC(NSiMe 3 ) 2 } 3 ]( I), [9] theP -C-O angle is 148.1-(3)8 8.T his suggests ar educed form of OCP À by Ni!PC backbonding,b ut the extent of OCP À reduction remains an open question since instability of this complex hampered its characterisation.…”

A General Synthesis of Phosphorus‐ and Arsenic‐Containing Analogues of the Thio‐ and Seleno‐cyanate Anions

“…[2b, 4-6] Related anions in which the nitrogen atom is replaced by ah eavier pnictogen element are also relatively rare.T he lithium salt of the 2-phosphaethynolate anion (PCO À )was first reported by Becker and co-workers in 1992, [7] however due to difficulties associated with its manipulation, its chemistry remained dormant for decades. [9][10][11] Theh eavier arsenic-containing ion, AsCO À ,w as first isolated in 2016 by our research group, [12] and promises to be as imilarly versatile reagent in chemical synthesis,h aving already been employed for the synthesis of several novel molecules. [8] Over the course of the last four years it has received significant attention as av iable precursor to rare (often unprecedented) phosphorus-containing compounds.…”

Synthese und Reaktivität von Nickel‐stabilisierten μ2:η2,η2‐P2‐, As2‐ und PAs‐Einheiten

“…[1] Gleichwohl war die Nutzbarkeit von PCO À fürd ie Synthese aufgrund der schwierigen Handhabung dieses Salzes sehr stark erschwert. [5] In den darauffolgenden Jahren fand das 2-Phosphaethinolat-Anion zahlreiche Anwendungen, unter anderem in der Synthese neuer Phosphane und phosphororganischer Verbindungen, [6,7] als Pseudohalogenid in der Koordinationssphäre von Hauptgruppen-, Übergangsmetall-und Actinoidverbindungen, [8][9][10] und in einigen Reaktionen, bei denen das Anion durch Decarbonylierung formal als Quelle eines monoanionischen Phosphidions (P À )g enutzt wurde. [4] Allerdings wurde erst im Jahr 2014 eine verlässliche und skalierbare Synthese dieses Anions verçffentlicht.…”