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Reactions of RSe–EMe 3 (E = Si, Ge, Sn, Pb) with XeF 2 — RSe–F Equivalents in the Fluoroselenenylation of Acetylenes [1]
Author(s) -
Poleschner Helmut,
Heydenreich Matthias,
Schilde Uwe
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(200006)2000:6<1307::aid-ejic1307>3.0.co;2-z
Subject(s) - chemistry , xenon difluoride , substituent , medicinal chemistry , acetylene , alkyne , aryl , reagent , yield (engineering) , alkyl , bond cleavage , triple bond , hydrolysis , stereochemistry , double bond , organic chemistry , catalysis , materials science , metallurgy
Selenides of the type R 1 Se–EMe 3 (E = Si, Ge, Sn, Pb) react with xenon difluoride by cleavage of the Se–E bond to yield the R 1 Se–F intermediate and the fluorides Me 3 E–F, whereas the Se–C bond in PhSe– t Bu (E = C) is stable against XeF 2 . The presence of R 1 Se–F intermediates is confirmed by addition to acetylenes (4‐octyne, 3‐hexyne). Thus, the fluoroselenenylation of acetylenes gives fluoro(organylseleno)olefins in preparative yields. In the cases of E = Si, Ge, Sn, and Pb, aryl and n ‐alkyl groups are suitable as the substituent R 1 . The X‐ray crystal structural analysis of ( E )‐3‐( p ‐carboxyphenylseleno)‐4‐fluorohex‐3‐ene – the first example of an uncharged fluoroselenoolefin synthesized from p ‐EtO 2 C–C 6 H 4 –Se–SnMe 3 , XeF 2 , and 3‐hexyne followed by an ester hydrolysis – shows that the addition of the selenenylfluoride intermediate to the acetylene proceeds via a trans ‐addition, as is known for the R 2 Se 2 –XeF 2 reagents.