Negative hyperconjugation control of acidities in α-trimethylsilyl substituted α-picolines: isolation of [Li{NC5H4-2-C(H)(SiMe3)2}{NC5H4-2-C(H)(SiMe3)}]2

Cameron Jones; Colin H.L. Kennard; Colin L. Raston; Graham Smith

doi:10.1016/0022-328X(90)85482-E

Negative hyperconjugation control of acidities in α-trimethylsilyl substituted α-picolines: isolation of [Li{NC₅H₄-2-C(H)(SiMe₃)₂}{NC₅H₄-2-C(H)(SiMe₃)}]₂

Cameron Jones
, Colin H.L. Kennard
, Colin L. Raston
, Graham Smith

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

16 Citations (Scopus)

Abstract

Isolation of [{Li(R′H)(R)}₂] (1) (R^- = NC₅H₄-2-CH(SiMe₃), R′H = NC₅H₄-2-RH(SiMe₃)₂), where R′H acts as an N-donor and R^- as an η³-aza-allyl unit to one metal centre and an N-bridge to the other (X-ray structure determination), and formation of [{Li(R)(tmeda)}₂] and R′H on treatment of (1) with tmeda (= N,N,N′,N′-tetramethylethylenediamine) establishes the relative solution thermodynamic acidities RH > R′H, rationalized by negative hyperconjugation in RH overriding extra polarization from two silicon centres in R′H.

Original language	English
Pages (from-to)	c39-c42
Journal	Journal of Organometallic Chemistry
Volume	396
Issue number	2-3
DOIs	https://doi.org/10.1016/0022-328X(90)85482-E
Publication status	Published - 16 Oct 1990
Externally published	Yes

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@article{0c290388540a48deb457511c7aef715e,

title = "Negative hyperconjugation control of acidities in α-trimethylsilyl substituted α-picolines: isolation of [Li\{NC5H4-2-C(H)(SiMe3)2\}\{NC5H4-2-C(H)(SiMe3)\}]2",

abstract = "Isolation of [\{Li(R′H)(R)\}2] (1) (R- = NC5H4-2-CH(SiMe3), R′H = NC5H4-2-RH(SiMe3)2), where R′H acts as an N-donor and R- as an η3-aza-allyl unit to one metal centre and an N-bridge to the other (X-ray structure determination), and formation of [\{Li(R)(tmeda)\}2] and R′H on treatment of (1) with tmeda (= N,N,N′,N′-tetramethylethylenediamine) establishes the relative solution thermodynamic acidities RH > R′H, rationalized by negative hyperconjugation in RH overriding extra polarization from two silicon centres in R′H.",

author = "Cameron Jones and Kennard, \{Colin H.L.\} and Raston, \{Colin L.\} and Graham Smith",

year = "1990",

month = oct,

day = "16",

doi = "10.1016/0022-328X(90)85482-E",

language = "English",

volume = "396",

pages = "c39--c42",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "2-3",

}

Negative hyperconjugation control of acidities in α-trimethylsilyl substituted α-picolines: isolation of [Li{NC₅H₄-2-C(H)(SiMe₃)₂}{NC₅H₄-2-C(H)(SiMe₃)}]₂. / Jones, Cameron; Kennard, Colin H.L.; Raston, Colin L. et al.
In: Journal of Organometallic Chemistry, Vol. 396, No. 2-3, 16.10.1990, p. c39-c42.

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

TY - JOUR

T1 - Negative hyperconjugation control of acidities in α-trimethylsilyl substituted α-picolines

T2 - isolation of [Li{NC5H4-2-C(H)(SiMe3)2}{NC5H4-2-C(H)(SiMe3)}]2

AU - Jones, Cameron

AU - Kennard, Colin H.L.

AU - Raston, Colin L.

AU - Smith, Graham

PY - 1990/10/16

Y1 - 1990/10/16

N2 - Isolation of [{Li(R′H)(R)}2] (1) (R- = NC5H4-2-CH(SiMe3), R′H = NC5H4-2-RH(SiMe3)2), where R′H acts as an N-donor and R- as an η3-aza-allyl unit to one metal centre and an N-bridge to the other (X-ray structure determination), and formation of [{Li(R)(tmeda)}2] and R′H on treatment of (1) with tmeda (= N,N,N′,N′-tetramethylethylenediamine) establishes the relative solution thermodynamic acidities RH > R′H, rationalized by negative hyperconjugation in RH overriding extra polarization from two silicon centres in R′H.

AB - Isolation of [{Li(R′H)(R)}2] (1) (R- = NC5H4-2-CH(SiMe3), R′H = NC5H4-2-RH(SiMe3)2), where R′H acts as an N-donor and R- as an η3-aza-allyl unit to one metal centre and an N-bridge to the other (X-ray structure determination), and formation of [{Li(R)(tmeda)}2] and R′H on treatment of (1) with tmeda (= N,N,N′,N′-tetramethylethylenediamine) establishes the relative solution thermodynamic acidities RH > R′H, rationalized by negative hyperconjugation in RH overriding extra polarization from two silicon centres in R′H.

UR - https://www.scopus.com/pages/publications/0002271172

U2 - 10.1016/0022-328X(90)85482-E

DO - 10.1016/0022-328X(90)85482-E

M3 - Article

AN - SCOPUS:0002271172

SN - 0022-328X

VL - 396

SP - c39-c42

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 2-3

ER -

Negative hyperconjugation control of acidities in α-trimethylsilyl substituted α-picolines: isolation of [Li{NC₅H₄-2-C(H)(SiMe₃)₂}{NC₅H₄-2-C(H)(SiMe₃)}]₂

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