Recent Developments in the Chemistry of Molecular Titanosiloxanes and Titanophosphonates

Davis, Paul M.; Murugavel, Ramaswamy

doi:10.1080/15533170500225540

Cited by 12 publications

(10 citation statements)

References 119 publications

(164 reference statements)

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“…Notice the prevalence of the Ti 3 O units in many of the titanium oxo-alkoxo clusters. 73,133,134 All of the known titanium phosphonates are listed in Table 9. 127−137 140 Another interesting alkoxide-bridged dinuclear zirconium phosphinate cage, [(OPr-i) 3 Zr(μ-OPr-i) 2 (μ-OPOPh 2 )Zr-(OPr-i) 2 Ph 2 P(O)(OH)], was obtained in the reaction of [Zr(OPr-i) 4 (i-PrOH)] 2 with Ph 2 P(O)(OH) (Scheme 40).…”

Section: Telluriummentioning

confidence: 99%

Molecular Metal Phosphonates

2015

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Section: Telluriummentioning

confidence: 99%

Molecular Metal Phosphonates

2015

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“…The N•••O distance in 2 is in the same order of magnitude as in 1. (3), crystallizes in two different forms 3 a and 3 b, which differ only slightly in their molecular dimensions. When crystallized directly from the reaction solution compound 3 a forms, which has no further solvent molecules in the crystal lattice, whereas 3 b forms when the solid reaction residue is redissolved in toluene and recrystallized (Figure 4).…”

Section: Structuresmentioning

confidence: 99%

“…The choice of the amine in the reaction is crucial. Whereas with diethyl amine the central ring is asymmetric with an oxygen respectively OÀ SiPh 2 À OÀ SiPh 2 À O linkage between the two aluminum atoms (1), with triethylamine the central ring has two diphenyl siloxane linkers, which can be shorter (2) or longer (3). With 1,4-diazabicyclo[2,2,0]octane exclusively one compound (4) can be isolated.…”

Section: Structuresmentioning

confidence: 99%

“…The incorporation of metallic elements in siloxanes or silesquioxanes has been widely studied since more than 70 years. [1][2][3][4] Within the molecular metallo-siloxanes the alumosiloxanes, also often addressed as molecular alumosiloxides, have attracted special attention because of their structural and chemical diversity. When aluminum is linked to one or several diphenyl siloxy groups, (Ph 2 SiO) n , cycles and polycycles can be generated with different geometries and with various applications.…”

Section: Introductionmentioning

confidence: 99%

“…[12,13,14] Because of its defined OÀ Al(OH)À O substructure I may also be used to mimic aluminum hydroxide surface reactivity as recently shown with the amino acid lysine. [15] Finally, this pentacyclic I as well as the bicyclic Al 2 (OSiPh 2 OSiPh 2 O) 3 • 2Q (II) [16] (see Figure 1), which can only be generated under strict exclusion of water and air, react with small amounts of water to form a multitude of polycyclic molecules which even incorporate complex building blocks like [Al 2 (OH) 8 ] 2À . [17] Intrigued by the transformations of the polycycles I and II into complex structures we had a closer look on the formation of cyclic compounds during hydrolysis and condensation of I and II.…”

Section: Introductionmentioning

confidence: 99%

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Transformations of the polycyclic Alumosiloxane Al₂(OSiPh₂OSiPh₂O)₃ into new Polycycles and Co(II) and In(III) derivatives of (Ph₂SiO)₈[Al(O)OH]₄

Veith

Sahin

Nadig

et al. 2021

Zeitschrift anorg allge chemie

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In the presence of water and amines the etherate of bicyclic Al 2 (OSiPh 2 OSiPh 2 O) 3 (II a) can be used to generate novel alumosiloxane polycycles like [O(Ph 2 SiOSiPh 2 ) O À ] 2 Al 2 O[O(Ph 2 SiOSiPh 2 )O] • 2 H 2 N + Et 2 (1), [O(Ph 2 SiOSiPh 2 ) O À ] 2 Al 2 [O(Ph 2 Si)O] 2 • 2 HN + Et 3 (2), [O(Ph 2 SiOSiPh 2 ) O À ] 2 Al 2 [O(Ph 2 SiOSiPh 2 )O] 2 • 2 HN + Et 3 (3 a, 3 b), which crystallizes in two different phases, and [O(Ph 2 SiOSiPh 2 ) O À ] 2 Al 2 [O(Ph 2 SiOSiPh 2 )O] 2 • 2 HN + (CH 2 CH 2 ) 3 N (4). As a common structural feature of these compounds two aluminum atoms which are incorporated in six-membered Al[O(SiPh 2 OSiPh 2 )O À ] rings are connected as spiro cyclic centers through oxygen and/ or siloxane bridges [(OSiPh 2 ) n O] (n = 1, 2) to form an assembly of three fused rings at the aluminum corners. The central ring is either eight-(1, 2) or twelve-membered (3, 4). Alkyl ammonium cations balance the charges and form hydrogen bridges to oxygen atoms of the six membered rings. The pentacyclic (Ph 2 SiO) 8 [Al(O)OH] 4 (I) can be used indirectly (addition of water) and directly as chelating ligand versus Co(II)Cl and In-CH 3 fragments as shown with the isolated and structurally characterized compounds (HN + Et 3 ) 2 {[(Ph 2 Si) 2 O 3 ][Al 4 (OH) 4 O 2 ](CoCl) 2 } 2À (5 a, 5 b) and (Ph 2 SiO) 8 [AlO(OH)] 2 [AlO 2 ] 2 (InCH 3 ) • 2 O(CH 2 ) 4 (6).

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Noncovalent Synthesis of Hierarchical Zinc Phosphates from a Single Zn₄O₁₂P₄ Double‐Four‐Ring Building Block: Dimensionality Control through the Choice of Auxiliary Ligands

Murugavel

Kuppuswamy

Gogoi

et al. 2010

Chemistry A European J

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In contrast to the well-known reaction of phosphonic acids RP(O)(OH)(2) with divalent transition-metal ions that yields layered metal phosphonates [RPO(3)M(H(2)O)](n), the 2,6-diisopropylphenyl ester of phosphoric acid, dippH(2), reacts with zinc acetate in methanol under ambient conditions to afford tetrameric zinc phosphate [(ArO)PO(3)Zn(MeOH)](4) (1). The coordinated methanol in 1 can be readily exchanged by stronger Lewis basic ligands at room temperature. This strategy opens up a new avenue for building double-four-ring (D4R) cubane-based supramolecular assemblies through strong intercubane hydrogen-bonding interactions. Seventeen pyridinic ligands have been used to synthesize as many D4R cubanes [(ArO)PO(3)Zn(L)](4) (2-18) from 1. The ligands have been chosen in such a way that the majority of them contain an additional functional group that could be used for noncovalent synthesis of extended structures. When the ligand does not contain any other hydrogen-bonding donor-acceptor sites (e.g., 2,4,6-trimethylpyridine (collidine)), zero-dimensional D4R cubanes have been obtained. The use of pyridine, lutidine, 2-aminopyridine, and 2,6-diaminopyridine, however, results in the formation of linear or zigzag one-dimensional assemblies of D4R cubanes through strong intermolecular C-H...O or N-H...O interactions. Construction of two-dimensional assemblies of zinc phosphates has been achieved by employing 2-hydroxypyridine or 2-methylimidazole as the exo-cubane ligand on zinc centers. The introduction of an alcohol side chain on the pyridinic ligand in such a way that the -CH(2)OH group cannot participate in intracubane hydrogen bonding (e.g., pyridine-3-methanol, pyridine-4-methanol, and 3,5-dimethylpyrazole-N-ethanol) leads to the facile noncovalent synthesis of three-dimensional framework structures. Apart from being useful as building blocks for noncovalent synthesis of zeolite-like materials, compounds 1-18 can also be thermolyzed at approximately 500 degrees C to yield high-purity zinc pyrophosphate (Zn(2)P(2)O(7)) ceramic material.

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Recent Developments in the Chemistry of Molecular Titanosiloxanes and Titanophosphonates

Cited by 12 publications

References 119 publications

Molecular Metal Phosphonates

Molecular Metal Phosphonates

Transformations of the polycyclic Alumosiloxane Al₂(OSiPh₂OSiPh₂O)₃ into new Polycycles and Co(II) and In(III) derivatives of (Ph₂SiO)₈[Al(O)OH]₄

Noncovalent Synthesis of Hierarchical Zinc Phosphates from a Single Zn₄O₁₂P₄ Double‐Four‐Ring Building Block: Dimensionality Control through the Choice of Auxiliary Ligands

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Recent Developments in the Chemistry of Molecular Titanosiloxanes and Titanophosphonates

Cited by 12 publications

References 119 publications

Molecular Metal Phosphonates

Molecular Metal Phosphonates

Transformations of the polycyclic Alumosiloxane Al2(OSiPh2OSiPh2O)3 into new Polycycles and Co(II) and In(III) derivatives of (Ph2SiO)8[Al(O)OH]4

Noncovalent Synthesis of Hierarchical Zinc Phosphates from a Single Zn4O12P4 Double‐Four‐Ring Building Block: Dimensionality Control through the Choice of Auxiliary Ligands

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Transformations of the polycyclic Alumosiloxane Al₂(OSiPh₂OSiPh₂O)₃ into new Polycycles and Co(II) and In(III) derivatives of (Ph₂SiO)₈[Al(O)OH]₄

Noncovalent Synthesis of Hierarchical Zinc Phosphates from a Single Zn₄O₁₂P₄ Double‐Four‐Ring Building Block: Dimensionality Control through the Choice of Auxiliary Ligands