Synthesis and Spectroscopic and Structural Investigations of the 2,3,4,5-Tetraethylarsolides and -stibolides of the Alkali Metals Sodium, Potassium, Rubidium, and Cesium

Abstract

The reduction of 1-chloro-2,3,4,5-tetraethylarsole and -stibole with the alkali metals sodium, potassium, rubidium, and cesium in 1,2-dimethoxyethane (DME) or TMEDA yields the corresponding 2,3,4,5-tetraethylarsolides (L)M-AsC 4 Et 4 [(L)M ) (TMEDA)Na 1a, (DME) 2/3 K 1b, (DME)Rb 1c, and (DME)Cs 1d] and 2,3,4,5-tetraethylstibolides (L)M-SbC 4 Et 4 [(L)M ) (DME) 1/2 Na 2a, (DME)Rb 2c, and (DME)Cs 2d]. These compounds are characterized by NMR spectroscopy and X-ray structure determinations. Whereas 1a crystallizes with discrete dimeric molecules, all other compounds form one-dimensional polymers. With the exception of the sodium derivatives, all polymers show exclusively η 5 -coordination of the arsolide and stibolide substituents. For the sodium compounds 1a and 1b also Na-As and Na-Sb σ-bonds, respectively, are observed.

Arsenic‐Mediated C−C Coupling of Cyanides Leading to Cyanido Arsazolide [AsC4N4]−

“…Only recently, neutral triazarsole heterocycles were isolated either by insertion of isonitriles into arsatriazanediyls [As( μ ‐NTer) 2 N] (Ter=2,6‐bis(2,4,6‐trimethylphenyl)phenyl, D d (As−N)=1.875 Å) and by making use of a [3+2] cycloaddition reaction between an arsaalkyne and an organic azide (species E d (As−N)=1.839 Å) . Arsolides of the type [R 4 C 4 As] − (R=Ph, Et) were described by Westerhausen et al . Neutral group 16 analogues of [AsC 4 N 4 ] − were obtained in the reaction of 2,3‐diaminomaleonitrile with ECl 4 (E=Se, Te) in the presence of organic bases …”

“…[15] While af ew cationic diazarsenium [16][17][18] (A [16] d(AsÀN) = 1.763, B [19] 1.803-1.814 )a nd neutral tetrazaarsole (d(AsÀN) = 1.784-1.805 ) [20] heterocycles are known (Scheme 3, species A-C), anionic diazarsolides are hitherto unknown. [22] Arsolides of the type [R 4 C 4 As] À (R=Ph, Et) were described by Westerhausen et al [23,24] Neutral group 16 analogues of [AsC 4 N 4 ] À were obtained in the reaction of 2,3-diaminomaleonitrile with ECl 4 (E=Se, Te )i nt he presence of organic bases. [22] Arsolides of the type [R 4 C 4 As] À (R=Ph, Et) were described by Westerhausen et al [23,24] Neutral group 16 analogues of [AsC 4 N 4 ] À were obtained in the reaction of 2,3-diaminomaleonitrile with ECl 4 (E=Se, Te )i nt he presence of organic bases.…”

Interpnictogen Compounds with Polarised Phosphorus–Element Bonds

“…Diphosphane 1 is formed through metathesis between N‐heterocyclic chlorophosphane 5a and lithium phospholide 6a 1. By analogy, coupling of 6a with chloroarsane 5b 5 and chlorostibane 5c 5 gave the expected products 2 , 3 with As–P and Sb–P bonds, and treatment of 5a with lithium arsolide 6b 6 produced 4 which is set apart from 2 by formal exchange of the two pnictogen atoms (Scheme ). In contrast, reaction of chlorophosphane 5a with the potassium stibolide [K(SbC 4 Et 4 )] ( 6c ) 7 was found to be messy, and we were unable to obtain an isolable product.…”

6 Nitrogen, phosphorus, arsenic, antimony and bismuth

“…137 The clusters Bi(Bi 2 (E = As, Sb), which were characterised by X-ray diffraction and NMR spectroscopy. 141 Theoretical calculations on the structures of GaAs 5 and InAs 5 have been performed and experimental evidence for these species as transports in the formation of GaAs and InAs has been proposed. 142 Theoretical studies of the electronic states of species TlE (E = As, Sb, Bi) 143 and molecules C n As 2 have been reported.…”