Facile Access to NaOC≡As and Its Use as an Arsenic Source To Form Germylidenylarsinidene Complexes

Abstract

A facile, one‐pot synthesis of [Na(OC≡As)(dioxane)x] (x=2.3–3.3) in 78 % yield is reported through the reaction of arsine gas with dimethylcarbonate in the presence of NaOtBu and 1,4‐dioxane. It has been employed for the synthesis of the first arsaketenyl‐functionalized germylene [LGeAsCO] (2, L=CH[CMeN(Dipp)]2; Dipp=2,6‐iPr2C6H3) from the reaction with LGeCl (1). Upon exposure to ambient light, 2 undergoes CO elimination to form the 1,3‐digerma‐2,4‐diarsacyclobutadiene [L2Ge2As2] (3), which contains a symmetric Ge2As2 ring with ylide‐like Ge=As bonds. Remarkably, the CO ligand located at the arsenic center of 2 can be exchanged with PPh3 or an N‐heterocyclic carbene iPrNHC donor (iPrNHC=1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) to afford the novel germylidenylarsinidene complexes [LGe‐AsPPh3] (4) and [LGe‐As(iPrNHC)] (5), respectively, demonstrating transition‐metal‐like ligand substitution at the arsinidene‐like As atom. The formation of 2–5 and their electronic structures have been studied by DFT calculations.

A soft molecular 2Fe–2As precursor approach to the synthesis of nanostructured FeAs for efficient electrocatalytic water oxidation

“…The facile synthesis and isolation of stable and robust arsaethynolate anion (AsCO À ) containing compounds were rst reported by Goicoechea and co-workers 48 and later, we reported the facile one-pot synthesis of the [Na(OCAs)(dioxane) x ] salt. 49 The AsCO À anion has been shown to react towards electrophiles and to form highly reactive arsinidenes through spontaneous or photocatalytic CO release. Thus, it serves as a building block towards new heterocyclic compounds, diarsenes, and terminal pnictides.…”

Recent advances in the chemistry of the phosphaethynolate and arsaethynolate anions

“…Reduction of 103 with [U(Tren TIPS )] yielded a mixed oxidation state diuranium–arsenido compound [{U(Tren TIPS )} 2 (μ-As)] ( 105 ) via a transient intermediate [U(Tren TIPS )(As)] on decarbonylation. SCXRD analysis of 105 confirmed the structural similarity to [{U(Tren TIPS )} 2 (μ-P)] − , 17 a ,95 except for the different bond lengths of U–As (2.943(4) and 2.889(4) Å) and the asymmetric U–As–U core, mirroring the mixed-valence uranium( iv / v ) nature.…”

“…In 2019, Scheer and Liddle et al isolated the first actinide-2-arsaethynolate complex [U(Tren TIPS )(OCAs)] ( 103 ; Tren TIPS = N(CH 2 CH 2 NSi i Pr 3 ) 3 ) using U( iv ) as a precursor. 93 The salt metathesis reaction of [U(Tren TIPS )(THF)][BPh 4 ] 94 ( 102 ) with [K(OCAs)] 17 a ,95 in THF led to the formation of novel complex 103 (Scheme 35). SCXRD analysis revealed the bond lengths of CAs, U–O and OC as 1.679(2) Å ( Σr cov = 1.66 Å), 96 2.3007(16) Å and 1.234(3) Å ( Σr cov = 1.24 Å), 96 respectively, with almost linear bond angles in O–C–As (178.9(2)°) and U–O–C (173.03(16)°), validating the linkage of the 2-arsaethynolate anion (AsC–O − ) via the oxygen atom.…”

Intercepting a Transient Phosphino‐Arsinidene

“…Albeit less stable, a labile anionic arsinidene [Na(18‐crown‐6)][Ter 2 SnAs] was observed in the association and decarbonylation of AsCO − with a bulky stannylene . Driess and co‐workers postulated that a germylenyl‐arsinidene was generated as a transient species in the formation of a Ge 2 As 2 heterocycle which could be trapped with Lewis bases prior to dimerisation . So far, the preparation of a free arsinidene has eluded the skills of chemists.…”

“…The latter was prepared by photolytic elimination of carbon monoxide from the corresponding phosphanyl‐phosphaketene. With AsCO − as a potentially suitable source of arsaketenes and As − now being available on a preparatively useful scale, we attempted the synthesis of the phosphino‐arsinidene F employing the bulky diazaphospholidine backbone utilised in the isolation of E .…”