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

Abstract

Sodium phosphaethynolate reacts with [MCl(PDI)] (M = Co, Ir; PDI = pyridinediimine) to give metallaphosphaketenes, which in the case of iridium rearranges into a dimetalladiphosphene.

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

“…[21] Der [P(IMes)] À -Ligand ist nahezu äquidistant zu beiden Nickelatomen (2.269 (1) (4b)). (7), Ni1-As1 2.3405 (13),N i1-As1' 2.3450 (16), C1-O1 1.127 (12), As1-As1 ' 2.3006(18),N i1···Ni1' 3.055 (2);C1-Ni1-C2 107.3(4), C1-Ni1-As1 95.9(3), C1-Ni1-As1' 154.5(3), C2-Ni1-As1 154.5(2), C2-Ni1-As1' 97.1(2), As1-Ni1-As1' 58.81 (5). Die As-As-Bindung (2.301 (2) ) ist um 0.225 länger als die P-P-Bindung in 1a,was mit dem erhçhten Kovalenzradius von Arsen einhergeht (r As Àr P = 0.12 ).…”

“…[13] Die resultierenden Spezies lassen sich thermisch und/ oder photolytisch zu vermutlich intermediären Phosphinidenen decarbonylieren, [14] die jedoch meist zu Verbindungen einer der beiden folgenden Kategorien dimerisieren: 1) Diphosphacyclobutadien-Analoga (A in Abbildung 1) und 2) Diphosphen-verbrückte Verbindungen (B, C und D in Abbildung 1). [13] Die resultierenden Spezies lassen sich thermisch und/ oder photolytisch zu vermutlich intermediären Phosphinidenen decarbonylieren, [14] die jedoch meist zu Verbindungen einer der beiden folgenden Kategorien dimerisieren: 1) Diphosphacyclobutadien-Analoga (A in Abbildung 1) und 2) Diphosphen-verbrückte Verbindungen (B, C und D in Abbildung 1).…”

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.…”

Terminal tungsten pnictide complex formation through pnictaethynolate decarbonylation

“…[31][32][33][34] Notable exceptions are the spontaneous decarbonylation of OCP − within the coordination sphere of iridium(I) or titanium(III) to yield a Ir I -P=P-Ir I dimer and a Ti IV 2 P 2 diamond core dimer, respectively. 11,12 The reaction between 1 and OCP − thus comprises the first documented example of spontaneous CO release to generate a terminal phosphide complex.…”