Cyclotriphosphazene [N3P3(2,2′-dioxybiphenyl)2-(4-pyridinoxy)2] and its halogen bonded complex with 1,4-diiodotetrafluorobenzene

Bertani, Roberta; Ghedini, Elena; Gleria, Mario; Liantonio, Rosalba; Marras, Giovanni; Metrangolo, Pierangelo; Meyer, Franck; Pilati, Tullio; Resnati, Giuseppe

doi:10.1039/b507263h

Cited by 17 publications

(8 citation statements)

References 27 publications

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“…The PO bonds that link the oxypyridine and biphenoxy units to the phosphazene skeleton are of normal length and are consistent with values reported for other related biphenoxy‐ or aryloxycyclotriphosphazenes 4a. 12, 32, 33, 34 All of the PN distances (average 1.579(2) Å), and the P‐N‐P (average 121.98(16)°) and N‐P‐N (average 118.29(14)°) angles lie within the expected ranges 35. Metalation does not cause any distortion in the cyclophosphazene ring skeleton.…”

Section: Resultssupporting

confidence: 84%

“…The previously reported crystal structure of the cyclotriphosphazene ligand I used in this work revealed an R,S configuration of the biphenyls around the phosphorus centers,32 the same as in the starting material gem ‐[N 3 P 3 (O 2 C 12 H 8 ) 2 Cl 2 ] 33. Variable‐temperature NMR spectroscopy studies were, however, not carried out, thus the occurrence of interconversion processes between stereoisomers of this cyclotriphosphazene at room temperature is still an open issue.…”

Section: Resultsmentioning

confidence: 53%

“…[30] Furthermore, it was indicated that in the solid-state noncovalent p-p stacking interactions between dioxybiphenyl groups are effective in the formation of an ordered polymer-like assembly due to the enantiomeric discrimination between the R and S moieties of the meso molecules. [31] The previously reported crystal structure of the cyclotriphosphazene ligand I used in this work revealed an R,S configuration of the biphenyls around the phosphorus centers, [32] the same as in the starting material gem-[N 3 P 3 -…”

Section: Introductionmentioning

confidence: 92%

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Metallocyclo‐ and Polyphosphazenes Containing Gold or Silver: Thermolytic Transformation into Nanostructured Materials

Jiménez

Laguna

Benouazzane

et al. 2009

Chemistry A European J

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A cyclotriphosphazene bearing two 4-oxypyridine groups on the same phosphorus atom, gem-[N(3)P(3)(O(2)C(12)H(8))(2)(OC(5)H(4)N-4)(2)] (I), and its analogous polymer [{NP(O(2)C(12)H(8))}(0.7){NP(OC(5)H(4)N-4)(2)}(0.3)](n) (II), have been used to prepare gold or silver, cyclic and polymeric, metallophosphazenes. The following complexes, gem-[N(3)P(3)(O(2)C(12)H(8))(2)(OC(5)H(4)N-4{ML})(2)] (ML=Au(C(6)F(5)) (1) or Au(C(6)F(5))(3) (2)), [N(3)P(3)(O(2)C(12)H(8))(2)(OC(5)H(4)N-4{AuPPh(3)})(2)][NO(3)](2) (3), and [N(3)P(3)(O(2)C(12)H(8))(2)(OC(5)H(4)N-4{AgPPh(2)R})(2)][SO(3)CF(3)](2) (R=Ph (4) or Me (5)) have been obtained. Complexes 1 and 4 are excellent models for the preparation of the analogous polymers [{NP(O(2)C(12)H(8))}(0.7){NP(OC(5)H(4)N-4{ML})(2)}(0.3)](n) (ML=Au(C(6)F(5)) (P1), Ag(OSO(2)CF(3))PPh(3) (P2)). All complexes have been characterized by elemental analysis, various spectroscopic methods, and mass spectrometry. The polymers were further investigated by thermochemical methods (thermogravimetric analysis) and differential scanning calorimetry. For compounds 1-5 and for the starting phosphazene I, a mixture of different stereoisomers may be expected. The stereochemistry in solution has been studied by variable-temperature NMR spectroscopy studies, which provided evidence for interconversion processes that involve changes in the chirality of a 2,2'-dioxybiphenyl group. A single-crystal X-ray analysis of the gold complex 2 confirmed not only the proposed structure, but also S,S and R,R configurations at the two biphenoxy-substituted phosphorus centers, in contrast to those observed for the precursor I. Pyrolysis of these new metallophosphazenes was also studied. Notably, pyrolysis of the gold derivatives gave macroporous metallic gold sponges without the requirement of either an external reducing agent or a porous support. These materials were all characterized by XRD, TEM, SEM, and energy-dispersive X-ray spectroscopy.

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Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 53%

Section: Introductionmentioning

confidence: 92%

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Metallocyclo‐ and Polyphosphazenes Containing Gold or Silver: Thermolytic Transformation into Nanostructured Materials

Jiménez

Laguna

Benouazzane

et al. 2009

Chemistry A European J

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“…[28] The electron-poor portion of the charge-transfer complex is generally an electron-deficient organic halide, and so 1,4-diiodotetrafluorobenzene has been used quite extensively. [12,15,16,18,24,29,30] Halogen bonding in which the halide is attached to a double or triple bond is known, but these systems have been the subject of much fewer studies. Polymeric chains result from the interaction between tetraiodoethylene (TIE) and diamines.…”

Section: Introductionmentioning

confidence: 99%

Molecular Assemblies from Imidazolyl‐Containing Haloalkenes and Haloalkynes: Competition between Halogen and Hydrogen Bonding

Bouchmella

Boury

Dutremez

et al. 2007

Chemistry A European J

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The structural characterization of molecular assemblies constructed from imidazolyl-containing haloalkenes and haloalkynes is reported. 1-(3-Iodopropargyl)imidazole (2) and 1-(2,3,3-triiodoallyl)imidazole (5) were synthesized from 1-propargylimidazole (1). In the solid state, these wholly organic modules self-assemble through N...I halogen-bonding interactions, thus giving rise to polymeric chains. The N...I interaction observed in 2 (d(N...I)=2.717 A, angle-spherical C(sp)-I...N=175.8 degrees) is quite strong relative to previously reported data. The N...I interaction in 5 (d(N...I)=2.901 A, angle-spherical C(sp2)-I...N=173.6 degrees) is weaker, in accordance with the order C(sp)-X<--base>C(sp2)-X<--base. Compound 5 was found to give a 1:1 cocrystal 4 with morpholinium iodide (6). In the X-ray crystal studies of 4, N...I halogen-bonding interactions similar to those observed in 5 were shown not to be present, as the arrangement of the molecules is governed by two interwoven hydrogen-bonding networks. The first network involves N-H...O interactions between nearby morpholinium cations, and the second network is based on N-H...N hydrogen bonding between morpholinium cations and imidazolyl groups. Both hydrogen-bonding schemes are charge-assisted. Halogen bonding is not completely wiped out, however, as the triiodoalkene fragment forms a halogen bond with an iodide anion in its vicinity (d(I...I)=3.470 A, angle-spherical C(sp2)-I...I=170.7 degrees). X-ray crystal studies of 6 show a completely different arrangement from that observed in 4, namely, N-H...O interactions are not present. In crystalline 6, morpholinium cations are interconnected through C-H...O bridges (d(H...O)=2.521 and 2.676 A), and the NH2+ groups interact with nearby iodide anions (d(H...I)=2.633 and 2.698 A).

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“…In this case the stereochemistry was recorded for both racemic (170 [179] and 171 [196]) and meso (172 [196], 173 [197], 174 [198]) diastereoisomers, although for a number of structures the stereogenic properties were not recorded for either racemic (175 [199], 176 [200], 177 [201] ) or meso (178 [202], 179 [200]) compounds. The bis-BP motif is very common in metallocyclophosphazenes but the stereogenic properties were only stated in one study where the racemic form of bis-BP was observed (180 [203]).…”

Section: Derivatives Of Bis-bp Cyclotriphosphazenementioning

confidence: 99%

Chiral configurations in cyclophosphazene chemistry

Uslu

Yeşilot

2015

Coordination Chemistry Reviews

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Cyclotriphosphazene [N3P3(2,2′-dioxybiphenyl)2-(4-pyridinoxy)2] and its halogen bonded complex with 1,4-diiodotetrafluorobenzene

Abstract: We report the crystal structures of the title cyclotriphosphazene and its 1 : 1 molecular complex with 1,4-diiodotetrafluorobenzene. The latter crystal structure selectively includes CCl 4 molecules in bulbous cavities.

Cited by 17 publications

References 27 publications

Metallocyclo‐ and Polyphosphazenes Containing Gold or Silver: Thermolytic Transformation into Nanostructured Materials

Metallocyclo‐ and Polyphosphazenes Containing Gold or Silver: Thermolytic Transformation into Nanostructured Materials

Molecular Assemblies from Imidazolyl‐Containing Haloalkenes and Haloalkynes: Competition between Halogen and Hydrogen Bonding

Chiral configurations in cyclophosphazene chemistry

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