Structure of organophosphorus compounds

Antipin, M. Yu.; Struchkov, Yu. T.; Matrosov, E. I.; Бондаренко, Н. А.; Tsvetkov, E. N.; Kabachnik, M. I.

doi:10.1007/bf00746436

Cited by 3 publications

(7 citation statements)

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“…The cations in 1 , 2 , and 4 that consist of Ph 3 PO molecules linked into dimeric or trimeric units by bridging H + or H 3 O + cations, respectively, are probably produced by hydrolysis of Ph 3 PX 2 due to atmospheric moisture, as suggested by Arens et al19c and Lane et al19e The formation of various anions from tellurium tetrahalides and the structural relationships between them have been explained by Krebs and Paulat,17f and are depicted in Scheme . It is not quite clear what factors determine the product distribution and isolation of the actual anions.…”

Section: Resultsmentioning

confidence: 92%

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The Reactions of Tellurium Tetrahalides with Triphenylphosphine under Ambient Conditions

et al. 2004

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The reactions of tellurium tetrahalides and triphenylphosphine in tetrahydrofuran have been carried out under ambient conditions and afford [(Ph(3)PO)(2)H](2)[Te(2)X(10)] [X = Cl (1), Br (2)] and [(Ph(3)PO)(3)(OH(3)])(2)[TeI(6)] (4). The X-ray structures of 1 and 2 show that they are isostructural and contain discrete [Te(2)X(10)](2-) anions exhibiting octahedral coordination around both tellurium atoms with one shared edge and [Ph(3)POH...OPPh(3)](+) cations that show strong hydrogen bonds (the O...O distances are 2.399 and 2.404 A for 1 and 2, respectively). The compound 4 is built up with discrete octahedral hexaiodotellurate anions and [(Ph(3)PO)(3)(OH(3))](+) cations. The reaction of TeBr(4) and PPh(3) also results in the formation of formally zwitterionic Ph(3)PO(CH(2))(4)TeBr(4) (3). This reaction involves an unprecedented THF ring opening in which the oxygen atom becomes bonded to the phosphorus atom of triphenylphosphine and the carbon atom at the other end of the five-atomic chain becomes bonded to the tellurium atom of TeBr(4). The ring opening of the solvent THF is also taking place in the reaction involving tellurium tetraiodide, as indicated by the formation of C(4)H(8)TeI(2) (5). The reaction may initially lead to Ph(3)PI(2) that reacts with THF yielding Ph(3)PO and ICH(2)(CH(2))(2)CH(2)I. The latter species reacts with elemental tellurium producing 5. Depending on the conditions upon crystallization, two polymorphs of C(4)H(8)TeI(2) (5a and 5b) are observed. While the molecular structures of the two forms are virtually identical, their packing and intermolecular contacts are different. Two further minor products (6a and 6b) were isolated in the reaction of TeI(4) and PPh(3): Both are formally 1:1 adducts of 5 and TeI(4), but they differ considerably in their structures. 6a can be formulated as [C(4)H(8)TeI(+)](2)[Te(2)I(10)(2-)] and 6b as [C(4)H(8)TeI(+)](2)(TeI(3)(+))(2)(I(-))(4). The latter compound exhibits framework similar to that of the tetramers in gamma- and delta-TeI(4).

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Section: Resultsmentioning

confidence: 92%

“…The {(Ph 3 PO) 2 H} + cation has been characterized on few occasions and has been shown to involve a strong hydrogen bond …”

Section: Referencesmentioning

confidence: 99%

The Reactions of Tellurium Tetrahalides with Triphenylphosphine under Ambient Conditions

et al. 2004

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“…There are also two 5) Å. 48 The structure for 9 R,R contains a planar pyridine N-oxide ring with two CMPO fragments bonded through the methine carbon atoms at the 2and 6-positions of the pyridine N-oxide ring. As in 7, the PO and CO bonds in each CMPO fragment are mutually syn to each other.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis, Lanthanide Coordination Chemistry, and Liquid–Liquid Extraction Performance of CMPO-Decorated Pyridine and Pyridine N-Oxide Platforms

et al. 2013

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Syntheses for a set of new ligands containing one or two carbamoylmethylphosphine oxide (CMPO) fragments appended to pyridine and pyridine N-oxide platforms are described. Molecular mechanics analyses for gas phase lanthanide-ligand interactions for the pyridine N-oxides indicate that the trifunctional NOPOCO molecules, 2-{[Ph2P(O)][C(O)NEt2]C(H)}C5H4NO (7) and 2-{[Ph2P(O)][C(O)NEt2]CHCH2}C5H4NO (8), and pentafunctional NOPOP'O'COC'O' molecules, 2,6-{[Ph2P(O)][C(O)NEt2]C(H)}2C5H3NO (9) and 2,6-{[Ph2P(O)][C(O)NEt2]CHCH2}2C5H3NO (10), should be able to adopt, with minimal strain, tridentate and pentadentate chelate structures, respectively. As a test of these predictions, selected lanthanide coordination chemistry of the N-oxide derivatives was explored. Crystal structure analyses reveal the formation of a tridentate NOPOCO chelate structure for a 1:1 Pr(III) complex containing 7 while 8 adopts a mixed bidentate/bridging monodentate POCO/NO binding mode with Pr(III). Tridentate and tetradentate chelate structures are obtained for several 1:1 complexes of 9 while a pentadentate chelate structure is observed with 10. Emission spectroscopy for one complex, [Eu(9)(NO3)3], in methanol, shows that the Eu(III) ion resides in a low-symmetry site. Lifetime measurements for methanol and deuterated methanol solutions indicate the presence of four methanol molecules in the inner coordination sphere of the metal ion, in addition to the ligand, with the nitrate anions most likely dissociated. The solvent extraction performance of 7-10 in 1,2-dichloroethane for Eu(III) and Am(III) in nitric acid solutions was analyzed and compared with the performance of 2,6-bis(di-n-octylphosphinoylmethyl)pyridine N-oxide (TONOPOP'O') and n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (OPhDiBCMPO) measured under identical conditions.

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“…This type of parallel-parallel-orthogonal conformation has been named 'orthogonal flipper' by Dance & Scudder (2000) and is also the conformation adopted in an analogous unfluorinated structure with FeBr 4 À as the counterion (corresponding torsion angles = 19.5, 27.3 and 83.2, and 19.5, 27.3 and 83.2 ;Lane et al, 1994). However, when the counter-ion is ClO 4 À , a rotor-type conformation is adopted (corresponding torsion angles = 29.9, 37.3 and 64.1, and 16.2, 30.0 and 42.7 ; Antipin et al, 1980). In the structure of (I), the orthogonal rings are opposite each other in the hydrogenbonded dimers and participate in face-to-face interactions.…”

Section: Commentmentioning

confidence: 99%

“…Because of this, and as the H atom was not found in the difference electron-density map, it has been fixed at the initial halfway position between the O atoms in this strong hydrogen bond (Table 2), with its displacement parameter refined freely. Although this is reasonable it may not be strictly correct, as asymmetric positioning of the H atom is common in even the strongest hydrogen bonds; see, for example, Konu & Chivers (2006) and Antipin et al (1980), who found that the OÁ Á ÁHÁ Á ÁO bond in [{(C 6 H 5 ) 3 P O} 2 H] + ÁClO 4 À changes from symmetric at room temperature to asymmetric on cooling.…”

Section: Commentmentioning

confidence: 99%

Hydrogen bis[tris(4-fluorophenyl)phosphane oxide] triiodide

et al. 2012

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In the title compound, C(36)H(25)F(6)O(2)P(2)(+)·I(3)(-), hydrogen-bonded [{(p-FC(6)H(4))(3)PO}(2)H](+) dimers assemble along the crystallographic c axis to form channels that house extended chains of triiodide anions. Although the I-I bond lengths of 2.9452 (14) and 2.9023 (15) Å are typical, the inter-ion I...I distance of 3.5774 (10) Å is unusually short. A posteriori modelling of nonmerohedral twinning about (100) has been only partially successful, achieving a reduction in the maximum residual electron density from 5.28 to 3.24 e Å(-3). The inclusion of two low-occupancy I-atom sites (total 1.7%), which can be interpreted as translational disorder of the triiodide anions along the channels, reduced the maximum residual electron density to 2.03 e Å(-3). The minor fractional contribution volume of the nonmerohedral twin domains refined to 0.24 and simultaneous refinement of the inversion twin domains showed the crystal to be a 0.5:0.5 inversion twin.

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Structure of organophosphorus compounds

Cited by 3 publications

References 8 publications

The Reactions of Tellurium Tetrahalides with Triphenylphosphine under Ambient Conditions

The Reactions of Tellurium Tetrahalides with Triphenylphosphine under Ambient Conditions

Synthesis, Lanthanide Coordination Chemistry, and Liquid–Liquid Extraction Performance of CMPO-Decorated Pyridine and Pyridine N-Oxide Platforms

Hydrogen bis[tris(4-fluorophenyl)phosphane oxide] triiodide

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