J 2014

Construction of Larger Molecular Aluminophosphate Cages from the Cyclic Four-Ring Building Unit

CHYBA, Jan, Zdeněk MORAVEC, Marek NEČAS, Sanjay MATHUR, Jiří PINKAS et. al.

Basic information

Original name

Construction of Larger Molecular Aluminophosphate Cages from the Cyclic Four-Ring Building Unit

Authors

CHYBA, Jan (203 Czech Republic, belonging to the institution), Zdeněk MORAVEC (203 Czech Republic, belonging to the institution), Marek NEČAS (203 Czech Republic, belonging to the institution), Sanjay MATHUR (276 Germany) and Jiří PINKAS (203 Czech Republic, guarantor, belonging to the institution)

Edition

Inorganic Chemistry, Spojené státy americké, American Chemical Society, Washington DC, 2014, 0020-1669

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10402 Inorganic and nuclear chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

Impact factor

Impact factor: 4.762

RIV identification code

RIV/00216224:14740/14:00075992

Organization unit

Central European Institute of Technology

DOI

UT WoS

000334092500062

Keywords in English

aluminophosphates; bis(trimethysiloxy)phosphoric acid; secondary building units

Tags

Tags

International impact, Reviewed
Změněno: 13/3/2018 10:20, doc. Mgr. Marek Nečas, Ph.D.

Abstract

V originále

New molecular aluminophosphates of different nuclearity are synthesized by a stepwise process and structurally characterized. The alkane elimination reaction of bis(trimethysiloxy)phosphoric acid, OP(OH)(OSiMe3)2, with trialkylalanes, AlR3 (R = Me, Et, iBu), provides the cyclic dimeric aluminophosphates, [(AlR2{m2-O2P(OSiMe3)2})2] (R = Me (1), Et (2), iBu (3)). Unsymmetrically substituted cyclic aluminophosphonate [(AlMe2{m2-O2P(OSiMe3)(cHex)})2] (cis/trans 4), is prepared by dealkylsilylation reaction of cHexP(O)(OSiMe3)2 with AlMe3. The molecules 1-4 containing the [Al2(m2-O2P)2] inorganic core are structural and spectroscopic models for the single four-ring (S4R) secondary building units (SBU) of zeolite frameworks. Compound 1 serves as a starting point in construction of larger molecular units by reactions with OP(OH)(OSiMe3)2 as a cage-extending reagent, and with diketones, such as Hhfacac (1,1,1,5,5,5-hexafluoropentan-2,4-dione) and Hacac (pentan-2,4-dione), as capping reagents. The reaction of 1 with four eq. of Hhfacac lead to new cyclic aluminophosphate [(Al(hfacac)2{m2-O2P(OSiMe3)2})2] (5), existing in two isomeric (D2 and C2h) forms. The reaction of 1 with two eq. of OP(OH)(OSiMe3)2 and one eq. of Hhfacac provides a molecular aluminophosphate [AlMe{Al(hfacac)}2{m3-O3P(OSiMe3)}2{m2-O2P(OSiMe3)2}2{OP(OSiMe3)3}] (6) while by adding first the Hhfacac and using three eq. of OP(OH)(OSiMe3)2, we isolate [Al{Al(hfacac)}2{m3-O3P(OSiMe3)}2{m2-O2P(OSiMe3)2}2H{OP(O)(OSiMe3)2}2] (7). These molecules contain units in their cores that imitate 4=1 SBU of zeolite frameworks. The reaction with the order of component mixing 1, Hhfacac, OP(OH)(OSiMe3)2 at the 1:2:2 molar ratio lead to the formation of a larger cluster [(Al(AlMe){Al(hfacac)}{m3-O3P(OSiMe3)}2{m2-O2P(OSiMe3)2}3)2] (8) containing both S4R and 4=1 structural units. Similarly, Hacac (pentan-2,4-dione) provides an isostructural [(Al(AlMe){Al(acac)}{m3-O3P(OSiMe3)}2{m2-O2P(OSiMe3)2}3)2] (9).

Links

ED1.1.00/02.0068, research and development project
Name: CEITEC - central european institute of technology
EE2.3.30.0037, research and development project
Name: Zaměstnáním nejlepších mladých vědců k rozvoji mezinárodní spolupráce
7AMB13DE006, research and development project
Name: Chemické syntézy nano-fosforečnanů kovů pomocí mikrovlných, sonochemických a elektrospinningových metod (Acronym: SYNPHOSO)
Investor: Ministry of Education, Youth and Sports of the CR