TY - JOUR

T1 - Affinity of xenon(II) and carbon in the (heptafluorocyclohexa-1,4-dien-1-yl)xenonium ion for fluoride ion and acetonitrile

AU - Semenov, S.G.

AU - Sigolaev, Yu.F.

PY - 2006/12

Y1 - 2006/12

N2 - The results of B3LYP&PCM quantum-chemical calculations confirmed the possibility for formation of fluoro(heptafluorocyclohexa-1,3-dien-1-yl)xenon and (octafluorocyclohex-3-en-1-ylidene)xenon from (heptafluorocyclohexa-1,4-dien-1- yl)xenonium in liquid acetonitrile. The Xe(II) and C2 atoms in the cation are characterized by a strong affinity for fluoride ion, but the Xe(II) atom binds acetonitrile molecule. The addition of F- to C2 in [XeC6F7]+ is more favorable (by 6 kcal/mol) than replacement of the fluorine atom on Xe(II) by MeCN molecule. The charge on the xenon atom in (octafluorocyclohex-3-en-1-ylidene)xenon is small, the Xe-C bond is weakened, and its cleavage leads to ring contraction to perfluoro(3-methylidenecyclopent-1-ene).

AB - The results of B3LYP&PCM quantum-chemical calculations confirmed the possibility for formation of fluoro(heptafluorocyclohexa-1,3-dien-1-yl)xenon and (octafluorocyclohex-3-en-1-ylidene)xenon from (heptafluorocyclohexa-1,4-dien-1- yl)xenonium in liquid acetonitrile. The Xe(II) and C2 atoms in the cation are characterized by a strong affinity for fluoride ion, but the Xe(II) atom binds acetonitrile molecule. The addition of F- to C2 in [XeC6F7]+ is more favorable (by 6 kcal/mol) than replacement of the fluorine atom on Xe(II) by MeCN molecule. The charge on the xenon atom in (octafluorocyclohex-3-en-1-ylidene)xenon is small, the Xe-C bond is weakened, and its cleavage leads to ring contraction to perfluoro(3-methylidenecyclopent-1-ene).

UR - http://www.scopus.com/inward/record.url?scp=33846156900&partnerID=8YFLogxK

U2 - 10.1134/S1070428006120062

DO - 10.1134/S1070428006120062

M3 - Article

AN - SCOPUS:33846156900

VL - 42

SP - 1789

EP - 1891

JO - Russian Journal of Organic Chemistry

JF - Russian Journal of Organic Chemistry

SN - 1070-4280

IS - 12

ER -