Template effects on the asymmetric cycloaddition reaction between 3,4-dimethyl-1-phenylarsole and diphenylvinylphosphine and their arsenic elimination reaction

Electrophilic As-functionalisation of σ-arsolido complexes

“…Both metal-complexed phosphole and arsole ligands are known to undergo [4 + 2] cycloadditions upon treatment with dienophiles. 26–28 For the former, this led to the formation of stable 9-phosphanorbornene and -norbornadiene complexes en route to the first examples of saturated phosphirane (RPC 2 R′ 4 ) and unsaturated phosphirene (RPC 2 R′ 2 ) complexes. 26 Voβ and Schenk treated the Group 6 pentacarbonyl arsole complexes [M(RAsC 4 Me 4 )(CO) 5 ] (M = Cr, W; R = Me, t Bu, Ph) with the electrophilic alkyne dimethylacetylene dicarboxylate (DMAD, MeO 2 CCCCO 2 Me) though only the corresponding tetramethyl- ortho -phthalate dimethylester was isolated and no 9-arsanorbornadiene complex was obtained.…”

“…27 Leung has, however, demonstrated the enantioselective [4 + 2] cyclo-additions of alkenes to palladium-coordinated arsoles. 28 It was therefore of interest whether arsoles bearing metal substituents might enter into pseudo -Diels–Alder processes with activated alkynes.…”

Nitrogen, phosphorus, arsenic, antimony and bismuth

“…Related studies in the cycloaddition between both coordinated and uncoordinated arsoles with PPh(CHQCH 2 ) have also been reported. 79 A study of the mechanism of vitamin B 12 derivative to transfer a methyl group to arsenic trioxide has been reported. 80 The structure of a number of pnictogen clusters with interstitial metal atoms, viz M@Pn 4+ (M = Ni, Pd, Pt; Pn = As, Sb, Bi) have been studied by DFT theory.…”

σ-Arsolido complexes

“…1 This mode of coordination is however occasionally implicit en route to the small number of known pentahapto -arsolyl complexes. 1 b ,2 Arsole complexes, in contrast are plentiful, 3 reflecting the modest basicity of the arsenic ‘lone’ pair which is to an only limited extent involved in the Hückel aromatic sextet. 4 We have recently explored the synthesis of bridging heterobimetallic arsolido complexes [MM′(μ-AsC 4 Me 4 )L n ] via the addition of metal reagents to the molybdenum σ-arsolyl complex [Mo(σ-AsC 4 Me 4 )(CO) 3 (η-C 5 H 5 )] ( 2c ) 5 which is an analogue of Abel's complex 2a .…”