Synthesis and Functionalization of Molecular Building Blocks
for Metallophosphates and -silicates

D 2002

Synthesis and Functionalization of Molecular Building Blocks for Metallophosphates and -silicates

PINKAS, Jiří, Zuzana BRLEJOVÁ, Jiří LÖBL, Jan KRATOCHVÍL, Herbert W. ROESKY et. al.

Basic information

Original name

Synthesis and Functionalization of Molecular Building Blocks for Metallophosphates and -silicates

Authors

PINKAS, Jiří (203 Czech Republic, guarantor), Zuzana BRLEJOVÁ (203 Czech Republic), Jiří LÖBL (203 Czech Republic), Jan KRATOCHVÍL (203 Czech Republic) and Herbert W. ROESKY (276 Germany)

Edition

1. vyd. San Feliu de Guixols, Spain, The Inorganic Side of Molecular Architecture - D3, p. 3-3, 1 pp. 2002

Publisher

European Science Foundation

Other information

Language

English

Type of outcome

Stať ve sborníku

Field of Study

10402 Inorganic and nuclear chemistry

Country of publisher

Spain

Confidentiality degree

není předmětem státního či obchodního tajemství

RIV identification code

RIV/00216224:14310/02:00006345

Organization unit

Faculty of Science

Keywords in English

molecular phosphonates; silicates; cubic molecules; nonhydrolytic sol-gel

Abstract

V originále

To gain an insight into possible cage/spacer combinations, we selected compounds of the cubic D4R type, [2,6-(i-Pr)2C6H3(Me3Si)NSi(O)3Ti(O-i-Pr)]4 (1), [Me2NAl(O)3P-t-Bu]4 (2), and [XAl(O)3PR]4 (3, X = Me, i-Bu, R = t-Bu, c-Hex), and studied the reactivity of their amido, alkoxo, and alkyl substituents with a series of protic reagents. Alcohols, silanols, phenols, and acids with different acidity and steric bulkiness were employed. While the dimethylamido groups in 2 are easily replaced, the bulky and less basic aryl(trimethylsilyl)amido groups in 1 resist substitution. Instead, the alkoxy groups in 1 are exchanged or the whole framework is destroyed in the reactions with strongly acidic reagents. A new model compound for the structural moiety P(OSi)1(OAl)3 found in silicoaluminophosphates (SAPO) was prepared by a dealkysilylation reaction of alumazene [2,6-(i-Pr)2C6H3NAlMe]3 with tris(trimethylsilyl)ester of phosphoric acid. The resulting (MeAl)[2,6-(i-Pr)2C6H3N]3{Al[OP(OSiMe3)3]}2(O3POSiMe3) (4) contains a heteroadamantane core and was characterized by analytical and spectroscopic methods and its molecular structure was established by a single crystal X-ray diffraction experiment. This new aluminophosphate could serve as the starting point for developing other structural units as it contains reactive groups.

Links

GA203/01/1533, research and development project

Name: Nové bezvodé metody přípravy fosfátových, silikátových, hybridních a oxidických materiálů

Investor: Czech Science Foundation, New Nonaqueous Routes to Phosphate, Silicate, Hybrid, and Oxide Materials

Citovat

PINKAS, Jiří, Zuzana BRLEJOVÁ, Jiří LÖBL, Jan KRATOCHVÍL and Herbert W. ROESKY. Synthesis and Functionalization of Molecular Building Blocks for Metallophosphates and -silicates. In The Inorganic Side of Molecular Architecture - D3. 1st ed. San Feliu de Guixols, Spain: European Science Foundation, 2002, p. 3-3.

@inproceedings{405049,
   author = {Pinkas, Jiří and Brlejová, Zuzana and Löbl, Jiří and Kratochvíl, Jan and Roesky, Herbert W.},
   address = {San Feliu de Guixols, Spain},
   booktitle = {The Inorganic Side of Molecular Architecture - D3},
   edition = {1.},
   keywords = {molecular phosphonates; silicates; cubic molecules; nonhydrolytic sol-gel},
   language = {eng},
   location = {San Feliu de Guixols, Spain},
   pages = {3-3},
   publisher = {European Science Foundation},
   title = {Synthesis and Functionalization of Molecular Building Blocks for Metallophosphates and -silicates},
   year = {2002}
}

TY  - JOUR
ID  - 405049
AU  - Pinkas, Jiří - Brlejová, Zuzana - Löbl, Jiří - Kratochvíl, Jan - Roesky, Herbert W.
PY  - 2002
TI  - Synthesis and Functionalization of Molecular Building Blocks for Metallophosphates and -silicates
PB  - European Science Foundation
CY  - San Feliu de Guixols, Spain
KW  - molecular phosphonates
KW  - silicates
KW  - cubic molecules
KW  - nonhydrolytic sol-gel
N2  - To gain an insight into possible cage/spacer combinations, we selected compounds of the cubic D4R type, [2,6-(i-Pr)2C6H3(Me3Si)NSi(O)3Ti(O-i-Pr)]4 (1), [Me2NAl(O)3P-t-Bu]4 (2), and [XAl(O)3PR]4 (3, X = Me, i-Bu, R = t-Bu, c-Hex), and studied the reactivity of their amido, alkoxo, and alkyl substituents with a series of protic reagents. Alcohols, silanols, phenols, and acids with different acidity and steric bulkiness were employed. While the dimethylamido groups in 2 are easily replaced, the bulky and less basic aryl(trimethylsilyl)amido groups in 1 resist substitution. Instead, the alkoxy groups in 1 are exchanged or the whole framework is destroyed in the reactions with strongly acidic reagents. A new model compound for the structural moiety P(OSi)1(OAl)3 found in silicoaluminophosphates (SAPO) was prepared by a dealkysilylation reaction of alumazene [2,6-(i-Pr)2C6H3NAlMe]3 with tris(trimethylsilyl)ester of phosphoric acid. The resulting (MeAl)[2,6-(i-Pr)2C6H3N]3{Al[OP(OSiMe3)3]}2(O3POSiMe3) (4) contains a heteroadamantane core and was characterized by analytical and spectroscopic methods and its molecular structure was established by a single crystal X-ray diffraction experiment. This new aluminophosphate could serve as the starting point for developing other structural units as it contains reactive groups.
ER  -

PINKAS, Jiří, Zuzana BRLEJOVÁ, Jiří LÖBL, Jan KRATOCHVÍL and Herbert W. ROESKY. Synthesis and Functionalization of Molecular Building Blocks for Metallophosphates and -silicates. In \textit{The Inorganic Side of Molecular Architecture - D3}. 1st ed. San Feliu de Guixols, Spain: European Science Foundation, 2002, p.~3-3.

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