Selective lithiation and crystal structures of G1-carbosilane dendrimers with dimethoxybenzene functionalities

Sjoerd Harder; Reinout Meijboom; John R. Moss

doi:10.1016/j.jorganchem.2003.12.047

Selective lithiation and crystal structures of G1-carbosilane dendrimers with dimethoxybenzene functionalities

Sjoerd Harder, Reinout Meijboom, John R. Moss

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

9 Citations (Scopus)

Abstract

Synthetic routes for the following dendrimers are described: Si[CH₂CH₂Si(Me)₂CH₂ -3,5-(MeO)₂-C₆H₃]₄ (2) and Si[CH₂CH₂Si(Me)₂-2,4-(MeO) ₂-C₆H₃]₄ (4). The crystal structures of these dendrimers have been determined by single crystal X-ray diffraction. One of the dendrimers (2) shows crystallographic S₄-symmetry and intramolecular C-H·O bonding, whereas the other (4) shows crystallographic C₂-symmetry and is imbedded in a zipper-like network of intermolecular C-H·O bonds. Direct lithiation of these dendrimers with n-BuLi in Et₂O yields complete and selective lithiation in the aryl ring between the methoxy substituents. However, dendrimer 2 is also partially lithiated in the benzylic group. For the solid state structure of such lithiated dendrimers, a diamond-type assembly is predicted.

Original language	English
Pages (from-to)	1095-1101
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	689
Issue number	7
DOIs	https://doi.org/10.1016/j.jorganchem.2003.12.047
Publication status	Published - 1 Apr 2004
Externally published	Yes

Keywords

Carbosilanes
Crystal engineering
Dendrimers
Hydrogen bonds
Lithium

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/j.jorganchem.2003.12.047

Cite this

@article{b45f35fc332a45d88d9a865d7e0f1166,

title = "Selective lithiation and crystal structures of G1-carbosilane dendrimers with dimethoxybenzene functionalities",

abstract = "Synthetic routes for the following dendrimers are described: Si[CH2CH2Si(Me)2CH2 -3,5-(MeO)2-C6H3]4 (2) and Si[CH2CH2Si(Me)2-2,4-(MeO) 2-C6H3]4 (4). The crystal structures of these dendrimers have been determined by single crystal X-ray diffraction. One of the dendrimers (2) shows crystallographic S4-symmetry and intramolecular C-H·O bonding, whereas the other (4) shows crystallographic C2-symmetry and is imbedded in a zipper-like network of intermolecular C-H·O bonds. Direct lithiation of these dendrimers with n-BuLi in Et2O yields complete and selective lithiation in the aryl ring between the methoxy substituents. However, dendrimer 2 is also partially lithiated in the benzylic group. For the solid state structure of such lithiated dendrimers, a diamond-type assembly is predicted.",

keywords = "Carbosilanes, Crystal engineering, Dendrimers, Hydrogen bonds, Lithium",

author = "Sjoerd Harder and Reinout Meijboom and Moss, {John R.}",

year = "2004",

month = apr,

day = "1",

doi = "10.1016/j.jorganchem.2003.12.047",

language = "English",

volume = "689",

pages = "1095--1101",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "7",

}

TY - JOUR

T1 - Selective lithiation and crystal structures of G1-carbosilane dendrimers with dimethoxybenzene functionalities

AU - Harder, Sjoerd

AU - Meijboom, Reinout

AU - Moss, John R.

PY - 2004/4/1

Y1 - 2004/4/1

N2 - Synthetic routes for the following dendrimers are described: Si[CH2CH2Si(Me)2CH2 -3,5-(MeO)2-C6H3]4 (2) and Si[CH2CH2Si(Me)2-2,4-(MeO) 2-C6H3]4 (4). The crystal structures of these dendrimers have been determined by single crystal X-ray diffraction. One of the dendrimers (2) shows crystallographic S4-symmetry and intramolecular C-H·O bonding, whereas the other (4) shows crystallographic C2-symmetry and is imbedded in a zipper-like network of intermolecular C-H·O bonds. Direct lithiation of these dendrimers with n-BuLi in Et2O yields complete and selective lithiation in the aryl ring between the methoxy substituents. However, dendrimer 2 is also partially lithiated in the benzylic group. For the solid state structure of such lithiated dendrimers, a diamond-type assembly is predicted.

AB - Synthetic routes for the following dendrimers are described: Si[CH2CH2Si(Me)2CH2 -3,5-(MeO)2-C6H3]4 (2) and Si[CH2CH2Si(Me)2-2,4-(MeO) 2-C6H3]4 (4). The crystal structures of these dendrimers have been determined by single crystal X-ray diffraction. One of the dendrimers (2) shows crystallographic S4-symmetry and intramolecular C-H·O bonding, whereas the other (4) shows crystallographic C2-symmetry and is imbedded in a zipper-like network of intermolecular C-H·O bonds. Direct lithiation of these dendrimers with n-BuLi in Et2O yields complete and selective lithiation in the aryl ring between the methoxy substituents. However, dendrimer 2 is also partially lithiated in the benzylic group. For the solid state structure of such lithiated dendrimers, a diamond-type assembly is predicted.

KW - Carbosilanes

KW - Crystal engineering

KW - Dendrimers

KW - Hydrogen bonds

KW - Lithium

UR - http://www.scopus.com/inward/record.url?scp=1542576279&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2003.12.047

DO - 10.1016/j.jorganchem.2003.12.047

M3 - Article

AN - SCOPUS:1542576279

SN - 0022-328X

VL - 689

SP - 1095

EP - 1101

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 7

ER -

Selective lithiation and crystal structures of G1-carbosilane dendrimers with dimethoxybenzene functionalities

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this