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- W4238640596 abstract "From the reaction of trimethylsilyl ylides with AsCl3 the dichloroarsanyl ylides 2 b and 5 b are obtained. As shown by X-ray structure determination, their AsCl2 groups deviate systematically from the symmetric orientation. This conformation enables an effective charge transfer from the ylide moiety to one of the As−Cl bonds, which as a consequence is up to 15 pm longer than the other. At the same time the length of the As−C bonds in 2 b and 5 b indicates a partial double bond. The effects observed here are of the same type as those observed for the corresponding dichlorophosphanyl ylides; they are, however, more pronounced. The 1:1 condensation of the bis(trimethylsilyl) ylide 3 and AsCl3 yields the oligomers (Ph3PCAsCl)2,3,4. The dimer 7 b has a diarsetane structure. HCl adds readily to one of its As−C bonds without opening it. The trimer and the tetramer are ionic. The cation of the trimer forms a six-membered ring with a delocalized arsenium/phosphonium charge, the cation of the tetramer forms a barrelane cage with a phosphonio substituent, and the anion is AsCl4− in both cases (10, 13). An arsa-phosphocyanine cation as in 10 is also part of the diphosphonio isoarsindolide tetrachloroarsenate(III) 12. The structures of 7 b⋅HCl, 10, and 13 reflect again an ylide to As−Cl charge transfer. The As−Cl bonds of 13 are by far the longest ones known for a chloroarsine (average 249 pm)." @default.
- W4238640596 created "2022-05-12" @default.
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- W4238640596 date "2000-09-18" @default.
- W4238640596 modified "2023-09-26" @default.
- W4238640596 title "Acyclic, Ring, and Cage As,C Compounds from Trimethylsilyl Ylides and AsCl<sub>3</sub>" @default.
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- W4238640596 doi "https://doi.org/10.1002/1521-3765(20001002)6:19<3531::aid-chem3531>3.0.co;2-v" @default.
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