Novel Organic-Soluble Molecular Titanophosphonates with Cage Structures Comparable to Titanium-Containing Silicates

Walawalkar, Mrinalini G.; Horchler, Sabine; Dietrich, Stefan; Chakraborty, Debashis; Roesky, Herbert W.; Schäfer, Martina; Schmidt, Hans‐Georg; Sheldrick, George M.; Murugavel, Ramaswamy

doi:10.1021/om971045k

Cited by 49 publications

(50 citation statements)

References 27 publications

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“…Interpretation of the 1 H NMR spectroscopic data was limited due to the high number of chemically similar groups. 2 (μ 2 -OiPr) 6 (OiPr) 8 (O 3 P-allyl) 6 The integrals fitted well, but the multiplicities and signal overlap led to very broad and indistinct signals. The 13 C NMR spectrum also shows five doublets for the allyl groups, but signal overlap again made it difficult to elucidate the symmetry of 2.…”

Section: Resultsmentioning

confidence: 98%

“…When TMS-allylPP was treated with Ti(OiPr) 4 in a 1:2 ratio in isopropyl alcohol, the cluster [Ti 8 (μ 3 -O) 2 (μ 2 -OiPr) 6 -(OiPr) 8 (O 3 P-allyl) 6 Cluster 2 was synthesized several times, and either triclinic (space group P1, denoted as 2) or monoclinic crystals (space group P2 1 /n, denoted as 2b) were obtained. The molecular structures are the same in both cases, and the bond lengths and angles are similar (only the values for 2 are given in Figure 2), but the packing of the clusters is different.…”

Section: Resultsmentioning

confidence: 99%

“…The reaction of TMS-XylPP and Ti(OiPr) 4 led to the formation of [Ti 4 O(OiPr) 8 (O 3 P-xyl) 3 (iPrOH)] (6; Figure 4). The structure is analogous to that of 1, the neutral ligand at the "capping" titanium atom being isopropyl alcohol (instead of dmso as in 1).…”

Section: Resultsmentioning

confidence: 99%

“…For comparison, Ti(OiPr) 4 was also treated with allylphosphonic acid to yield a Ti 4 cluster. The reaction of Ti(OiPr) 4 with the bulky bis(trimethylsilyl) 2-naphthylmethyphosphonate did not yield an oxo cluster but instead the phosphonate-substituted titanium alkoxide Ti 4 (OiPr) 8 (O 3 PCH 2 naphthyl) 4 .…”

Section: Introductionmentioning

confidence: 97%

“…A few phosphonate-and phosphinate-substituted oxo clusters have been obtained by the reaction of titanium alkoxides with some phosphonic or phosphinic acids. [5][6][7] The formation of oxo groups in the clusters was attributed to residual moisture in the solvents or phosphonic acids [5][6][7][8] rather than to an esterification reaction. The compounds obtained by reaction with phosphinates had similar structures to comparable carboxylatesubstituted derivatives.…”

Section: Introductionmentioning

confidence: 99%

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Influence of the Phosphonate Ligand on the Structure of Phosphonate‐Substituted Titanium Oxo Clusters

2013

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The reaction of titanium isopropoxide, Ti(OiPr)4, with bis(trimethylsilyl) phosphonates has led to structures containingTi3O units [= Ti3(μ3‐O)(μ2‐OiPr)3(OiPr)3(O3PR)3] as the basic structural motif. This unit can be capped by a single Ti(OiPr)2L group (L = neutral ligand) through phosphonate bridges (for R = xylyl), or sandwich‐like structures can be formed with two Ti3O units bonded to a central Ti atom (for R = CH2CH2CH2Cl or benzyl). For R = allyl or ethyl, dimeric clusters were formed in which two Ti4 cluster units are bridged by isopropyl phosphonate ligands. For comparison, Ti(OiPr)4 was also treated with allylphosphonic acid to yield a Ti4 cluster. The reaction of Ti(OiPr)4 with the bulky bis(trimethylsilyl) 2‐naphthylmethyphosphonate did not yield an oxo cluster but instead the phosphonate‐substituted titanium alkoxide Ti4(OiPr)8(O3PCH2naphthyl)4.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

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Influence of the Phosphonate Ligand on the Structure of Phosphonate‐Substituted Titanium Oxo Clusters

2013

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Controlling the Structure of Manganese(II) Phosphates by the Choice and Ratio of Organophosphate and Auxiliary Ligands

Murugavel

Kuppuswamy

Gogoi

et al. 2008

Chemistry An Asian Journal

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Tetranuclear manganese(II) phosphates [Mn(dipp)(bpy)](4)4 H(2)O (1) and [Mn(4)(dmpp)(2)(dmppH)(4)(bpy)(4)(H(2)O)(2)]H(2)O (2) have been prepared from Mn(OAc)(2)4 H(2)O and 2,6-diisopropylphenyl phosphate (dippH(2)) or 2,6-dimethylphenyl phosphate (dmppH(2)) in the presence of 2,2'-bipyridine (bpy). In contrast, the reaction between [Mn(bpy)(2)(OAc)(ClO(4))]H(2)O and dippH(2) affords [Mn(bpy)(2)(dippH)](2)2 ClO(4)2 CH(3)OH (3). The reactions of Mn(OAc)(2)4 H(2)O, dippH(2), and pyridine (py) or 3,5-dimethylpyrazole (dmpz) in CH(3)CN under reflux afford hexanuclear complexes [Mn(6)(dipp)(6)(py)(8)]2CH(3)CN (4) and [Mn(6)(dipp)(6)(dmpz)(6)(AcOH)(2)]2 H(2)O (5), respectively. Although compounds 1 and 2 are tetrameric, the former is a closed cubane-like structure resembling the D4R secondary building unit of zeolites, whereas the latter exists in a staircase structure with fused Mn(2)O(4)P(2) rings. The core structure of 3 contains a Mn(2)O(4)P(2) eight-membered ring that resembles the S4R building block of zeolites. Single-crystal X-ray diffraction studies reveal that compounds 4 and 5 have a similar core structure and differ from each other by the neutral ligands coordinated to manganese ions. All six phosphate ligands exist in a doubly deprotonated [(RO)PO(3) (2-)] form and exhibit two types of binding modes [5.222] and [3.111]. An interesting feature of compounds 1-5 is that although they are oligonuclear complexes, there is an absence of oxido bridges. The magnetic properties of compounds 1-5 have been investigated in the temperature range 5-298 K, and it was found that all the compounds obey the Curie law.

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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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Novel Organic-Soluble Molecular Titanophosphonates with Cage Structures Comparable to Titanium-Containing Silicates

Cited by 49 publications

References 27 publications

Influence of the Phosphonate Ligand on the Structure of Phosphonate‐Substituted Titanium Oxo Clusters

Influence of the Phosphonate Ligand on the Structure of Phosphonate‐Substituted Titanium Oxo Clusters

Controlling the Structure of Manganese(II) Phosphates by the Choice and Ratio of Organophosphate and Auxiliary Ligands

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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Novel Organic-Soluble Molecular Titanophosphonates with Cage Structures Comparable to Titanium-Containing Silicates

Cited by 49 publications

References 27 publications

Influence of the Phosphonate Ligand on the Structure of Phosphonate‐Substituted Titanium Oxo Clusters

Influence of the Phosphonate Ligand on the Structure of Phosphonate‐Substituted Titanium Oxo Clusters

Controlling the Structure of Manganese(II) Phosphates by the Choice and Ratio of Organophosphate and Auxiliary Ligands

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