Universität zu Köln

Chyba, Jan ORCID: 0000-0002-1273-5632, Moravec, Zdenek ORCID: 0000-0003-4377-3575, Necas, Marek, Mathur, Sanjay and Pinkas, Jiri ORCID: 0000-0002-6234-850X (2014). Construction of Larger Molecular Aluminophosphate Cages from the Cyclic Four-Ring Building Unit. Inorg. Chem., 53 (7). S. 3753 - 3763. WASHINGTON: AMER CHEMICAL SOC. ISSN 1520-510X

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Abstract

New molecular aluminophosphates of different nuclearity are synthesized by a stepwise process and structurally characterized. The alkane elimination reaction of bis(trimethylsiloxy)phosphoric acid, OP-(OH)(OSiMe3)(2), with trialkylalanes, AlR3 (R = Me, Et, Bu-i), provides the cyclic dimeric aluminophosphates, [(AlR2{mu(2)-O2P(OSiMe3)(2)})(2)) (R = Me (1), Et (2), Bu-i (3)). Unsymmetrically substituted cyclic aluminophosphonate [(AlMe2{mu(2)-O2P(OSiMe3)((c)Hex)})(2)] (cis/trans-4) is prepared by dealkylsilylation reaction of (c)HexP(O)(OSiMe3)(2) with AlMe3. Molecules 1-4 containing the [Al-2(mu(2)-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. Reaction of 1 with 4 equiv of Hhfacac leads to new cyclic aluminophosphate [(Al(hfacac)(2){mu(2)-O2P(OSiMe3)(2)})(2)] (5), existing in two isomeric (D-2 and C-2h) forms. Reaction of 1 with 2 equiv of OP(OH)(OSiMe3)(2) and 1 equiv of Hhfacac provides a molecular aluminophosphate [AlMe{Al(hfacac)}(2){mu(3)-O3P(OSiMe3)}(2){mu(2)-O2P(OSiMe3)(2)}(2){OP-(OSiMe3)(3)}] (6), while by adding first the Hhfacac and using 3 equiv of OP(OH)(OSiMe3)(2) we isolate [Al{Al(hfacac)}(2){mu(3)-O3P(OSiMe3)}(2){mu(2)-O2P(OSiMe3)(2)}(2)H{OP(O)(OSiMe3)(2)}(2)] (7). These molecules contain units in their cores that imitate 4=1 SBU of zeolite frameworks. Reaction with the order of component mixing 1, Hhfacac, OP(OH)(OSiMe3)(2) at a 1:2:2 molar ratio lead to formation of a larger cluster [(Al(AlMe){Al(hfacac)}{mu(3)-O3P(OSiMe3)}(2){mu(2)-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)}{mu(3)-O3P(OSiMe3)}(2){mu(2)-O2P(OSiMe3)(2)}(3))(2)] (9). Both molecules display Al centers in three different coordination environments.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Chyba, Jan UNSPECIFIED orcid.org/0000-0002-1273-5632 UNSPECIFIED Moravec, Zdenek UNSPECIFIED orcid.org/0000-0003-4377-3575 UNSPECIFIED Necas, Marek UNSPECIFIED UNSPECIFIED UNSPECIFIED Mathur, Sanjay UNSPECIFIED UNSPECIFIED UNSPECIFIED Pinkas, Jiri UNSPECIFIED orcid.org/0000-0002-6234-850X UNSPECIFIED
URN:	urn:nbn:de:hbz:38-440826
DOI:	10.1021/ic500083a
Journal or Publication Title:	Inorg. Chem.
Volume:	53
Number:	7
Page Range:	S. 3753 - 3763
Date:	2014
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1520-510X
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language METAL PHOSPHATES; MODEL COMPOUNDS; ALUMINUM; CRYSTAL; CHEMISTRY; CLUSTERS; GALLIUM; NMR; PHOSPHONATES; PRECURSORS Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/44082