Carbon-fluorine bond activation in perfluorobenzonitrile by LiN(SiMe3)2. Synthesis of (Me3Si)2NC6F4CN-4 and crystal structure of LiN(C6F4CN-4)2·2C4H 8O

Michal Shmulinson; Astrid Pilz; Moris S. Eisen

doi:10.1039/a700682i

Carbon-fluorine bond activation in perfluorobenzonitrile by LiN(SiMe₃)₂. Synthesis of (Me₃Si)₂NC₆F₄CN-4 and crystal structure of LiN(C₆F₄CN-4)₂·2C₄H ₈O

Michal Shmulinson, Astrid Pilz, Moris S. Eisen^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

The reaction of C₆F₅CN with the dimeric lithium salt [Li(NSiMe₃)·Et₂O]₂ yielded a 11:9 mixture of (Me₃Si)₂NC₆F₄CN-41 and LiN(C₆F₄CN-4)₂·2thf, respectively (thf = tetrahydrofuran). The compounds were characterized spectroscopically and complex 2 by crystal structure determination. The central lithium forms a distorted trigonal bipyramid the apical position of which is filled by a nitrile nitrogen of an adjacent molecule, inducing chains running parallel to the b-direction of the crystal. The driving force for the production of 1 and 2 is the elimination of LiF and SiMe₃F, respectively. The calculated enthalpy for formation of 2 is more favourable compared to that for formation of 1, although the similar yields indicate that similar enthalpies of activation apply to both systems.

Original language	English
Pages (from-to)	2483-2486
Number of pages	4
Journal	Journal of the Chemical Society. Dalton Transactions
Issue number	14
DOIs	https://doi.org/10.1039/a700682i
State	Published - 21 Jul 1997
Externally published	Yes

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title = "Carbon-fluorine bond activation in perfluorobenzonitrile by LiN(SiMe3)2. Synthesis of (Me3Si)2NC6F4CN-4 and crystal structure of LiN(C6F4CN-4)2·2C4H 8O",

abstract = "The reaction of C6F5CN with the dimeric lithium salt [Li(NSiMe3)·Et2O]2 yielded a 11:9 mixture of (Me3Si)2NC6F4CN-41 and LiN(C6F4CN-4)2·2thf, respectively (thf = tetrahydrofuran). The compounds were characterized spectroscopically and complex 2 by crystal structure determination. The central lithium forms a distorted trigonal bipyramid the apical position of which is filled by a nitrile nitrogen of an adjacent molecule, inducing chains running parallel to the b-direction of the crystal. The driving force for the production of 1 and 2 is the elimination of LiF and SiMe3F, respectively. The calculated enthalpy for formation of 2 is more favourable compared to that for formation of 1, although the similar yields indicate that similar enthalpies of activation apply to both systems.",

author = "Michal Shmulinson and Astrid Pilz and Eisen, {Moris S.}",

year = "1997",

month = jul,

day = "21",

doi = "10.1039/a700682i",

language = "英语",

pages = "2483--2486",

journal = "Journal of the Chemical Society. Dalton Transactions",

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publisher = "Royal Society of Chemistry",

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T1 - Carbon-fluorine bond activation in perfluorobenzonitrile by LiN(SiMe3)2. Synthesis of (Me3Si)2NC6F4CN-4 and crystal structure of LiN(C6F4CN-4)2·2C4H 8O

AU - Shmulinson, Michal

AU - Pilz, Astrid

AU - Eisen, Moris S.

PY - 1997/7/21

Y1 - 1997/7/21

N2 - The reaction of C6F5CN with the dimeric lithium salt [Li(NSiMe3)·Et2O]2 yielded a 11:9 mixture of (Me3Si)2NC6F4CN-41 and LiN(C6F4CN-4)2·2thf, respectively (thf = tetrahydrofuran). The compounds were characterized spectroscopically and complex 2 by crystal structure determination. The central lithium forms a distorted trigonal bipyramid the apical position of which is filled by a nitrile nitrogen of an adjacent molecule, inducing chains running parallel to the b-direction of the crystal. The driving force for the production of 1 and 2 is the elimination of LiF and SiMe3F, respectively. The calculated enthalpy for formation of 2 is more favourable compared to that for formation of 1, although the similar yields indicate that similar enthalpies of activation apply to both systems.

AB - The reaction of C6F5CN with the dimeric lithium salt [Li(NSiMe3)·Et2O]2 yielded a 11:9 mixture of (Me3Si)2NC6F4CN-41 and LiN(C6F4CN-4)2·2thf, respectively (thf = tetrahydrofuran). The compounds were characterized spectroscopically and complex 2 by crystal structure determination. The central lithium forms a distorted trigonal bipyramid the apical position of which is filled by a nitrile nitrogen of an adjacent molecule, inducing chains running parallel to the b-direction of the crystal. The driving force for the production of 1 and 2 is the elimination of LiF and SiMe3F, respectively. The calculated enthalpy for formation of 2 is more favourable compared to that for formation of 1, although the similar yields indicate that similar enthalpies of activation apply to both systems.

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U2 - 10.1039/a700682i

DO - 10.1039/a700682i

M3 - 文章

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SP - 2483

EP - 2486

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

IS - 14

ER -

Carbon-fluorine bond activation in perfluorobenzonitrile by LiN(SiMe₃)₂. Synthesis of (Me₃Si)₂NC₆F₄CN-4 and crystal structure of LiN(C₆F₄CN-4)₂·2C₄H ₈O

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