Synthese, IR‐ und EPR‐Spektren sowie die Kristallstruktur von HPPh3[WOCl4(OPPh3)]

Kersting, Meinolf; Friebel, C.; Dehnicke, Kurt; Krestel, Magda; Allmann, R.

doi:10.1002/zaac.19885630111

Cited by 11 publications

(9 citation statements)

References 21 publications

(2 reference statements)

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“…In addition to the characteristic ν BH absorption at 2578 cm –1 , an additional albeit weak absorption was observed at 2457 cm –1 . Given this appears above the range associated with ν WH absorptions for terminal hydride ligands, we tentatively assign it to the ν PH mode by comparison with that observed (2415 cm –1 ) for [HPPh 3 ][WOCl 4 (OPPh 3 )] . Furthermore, the values calculated (ν PH = 2402, ν CO = 2004, 1946 cm –1 , k CK = 15.73 N cm –1 , vide infra ) agree well, given the caveats associated with comparisons between experimental solid-state and calculated gas-phase data for ionic species.…”

Section: Resultssupporting

confidence: 61%

Synthesis and Reactivity of Phosphinocarbyne Complexes

2014

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The successive treatment of [W(CBr)(CO)2(Tp*)] (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with n BuLi and ClPPh2 affords the phosphinocarbyne complex [W(CPPh2)(CO)2(Tp*)] (1), DFT interrogation of which suggests that reactions with electrophiles may involve both the phosphorus atom and/or the metal–carbon multiple bond. This is borne out in reactions of 1 with a variety of electrophilic reagents. With iodomethane or dimethylsulfide borane, electrophilic attack occurs exclusively at phosphorus to afford the compounds [W(CPMePh2)(CO)2(Tp*)]I ([2]I) and [W{CP(BH3)Ph2}(CO)2(Tp*)] (3). The reaction of 1 with sulfur affords both the thiophosphorylcarbyne complex [W{CP(S)Ph2}(CO)2(Tp*)] (4) and the thioacyl complex [W{η2-SCP(S)Ph2}(CO)2(Tp*)] (5), though 4 fails to react with sulfur to provide 5. In a similar manner, the complexes 2 and 3 also fail to react with sulfur, indicating that increasing the valance of the phosphorus center of 1 deactivates the WC bond toward further attack. Addition of selenium to 1 occurs exclusively at phosphorus to afford [W{CP(Se)Ph2}(CO)2(Tp*)] (6) with no indication of selenoacyl formation. Reversible protonation of 1 with HBF4 in diethyl ether precipitates the phosphoniocarbyne salt [W(CPHPh2)(CO)2(Tp*)]BF4, [8]BF4, which, however, on dissolution in dichloromethane rearranges irreversibly to the thermodynamic (ΔG cacld = 22.4 kJmol–1) phosphinocarbene isomer [W(η2CHPPh2)(CO)2(Tp*)]BF4, [9]BF4.

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Section: Resultssupporting

confidence: 61%

Synthesis and Reactivity of Phosphinocarbyne Complexes

2014

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“…177.1 6In the IR spectrum of 3 (solid state), the [W=O] band has been found at 983 cm −1 . The EPR spectrum (in CH 2 Cl 2 , Figure 5) well matches the computed spectrum (experimental g iso = 1.77461, linewidth = 94.48 G [20]; calculated parameters: g ⁄⁄ = 1.78842, g ⊥ = 1.77457, g iso = 1.77919). The calculated structure and the spin density distribution of 3 indicate that the electron spin density is equally distributed on the two W atoms, each of them in a +5.5…”

Section: Reactivity Of Wcl 6 With Tetrahydrofuransupporting

confidence: 70%

“…Moreover, the presence of Cl(CH 2 ) 4 O(CH 2 ) 4 Cl and Cl(CH 2 ) 4 Cl in dichloromethane mixtures (thf/W ratio = ca. 4 to 20) was pointed out. The ether Cl(CH 2 ) 4 O(CH 2 ) 4 Cl is presumably the result of coupling of two thf units mediated by a tungsten centre, and may be involved in the formation of oxo-bridged complexes like 3.…”

Section: Reactivity Of Wcl 6 With Tetrahydrofuranmentioning

confidence: 98%

The reactivity of tungsten hexachloride with tetrahydrofuran and 2-methoxyethanol

et al. 2016

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The ring opening polymerization reaction of tetrahydrofuran (thf) by WCl6 was investigated under different conditions, and the polymeric material was characterized by NMR and SEC (Size Exclusion Chromatography) analyses. The mixed valence complex [(thf)2(μ-H)][WOCl3(thf)2(μ-O)], 3, was isolated from the reactions of WCl6 with 4–8 equivalents of thf in dichloromethane at room temperature, and crystallographically characterized. The formation of 3 was preceded by that of WOCl4(thf), 2, while Cl(CH2)4Cl and Cl(CH2)4O(CH2)4Cl were identified as the prevalent organic side products. The 1:1 M reaction of WCl6 with MeO(CH2)2OH, in CH2Cl2 at room temperature, afforded the complexes (WOCl4)2(μ-κ2-1,4-dioxane), 4, and WCl5(OCH2CH2OMe), 5, in admixture with Cl(CH2)2Cl, MeO(CH2)2OMe and MeCl. Also complex 4, resulting from a [Formula presented] bond forming process, was characterized by X-ray crystallography

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“…COSMO is employed with the default parameters to compensate for the negative charge, , and the x2c-QZVPall-2c basis set is chosen for consistency with our previous studies on the HFC constant . Errors are measured with respect to the experimental findings − collected in ref .…”

Section: Computational Detailsmentioning

confidence: 99%

Quasi-Relativistic Calculation of EPR g Tensors with Derivatives of the Decoupling Transformation, Gauge-Including Atomic Orbitals, and Magnetic Balance

Franzke

2022

J. Chem. Theory Comput.

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We present an exact two-component (X2C) ansatz for the EPR g tensor using gauge-including atomic orbitals (GIAOs) and a magnetically balanced basis set expansion. In contrast to previous X2C and four-component relativistic ansaẗze for the g tensor, this implementation results in a gauge-origin-invariant formalism. Furthermore, the derivatives of the relativistic decoupling matrix are incorporated to form the complete analytical derivative of the X2C Hamiltonian. To reduce the associated computational costs, we apply the diagonal local approximation to the unitary decoupling transformation (DLU). The quasirelativistic X2C and DLU-X2C Hamiltonians accurately reproduce the results of the parent four-component relativistic theory when accounting for two-electron picture-change effects with the modified screened nuclear spin−orbit approximation in the respective one-electron integrals and integral derivatives. According to our benchmark studies, the uncontracted Dyall and segmented-contracted Karlsruhe x2c-type basis sets perform well when compared to large even-tempered basis sets. Moreover, (range-separated) hybrid density functional approximations such as LC-ωPBE and ωB97X-D are needed to match the experimental findings. The impact of the GIAOs depends on the distribution of the spin density, and their use may change the Δg shifts by 10−50% as shown for [(C 5 Me 5 ) 2 Y(μ-S) 2 Mo(μ-S) 2 Y(C 5 Me 5 ) 2 ] − . Routine calculations of large molecules are possible with widely available and comparably low-cost hardware as demonstrated for [Pt(C 6 Cl 5 ) 4 ] − with 3003 basis functions and three spin-(1/2) La(II) and Lu(II) compounds, for which we observe good agreement with the experimental findings.

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Synthese, IR‐ und EPR‐Spektren sowie die Kristallstruktur von HPPh₃[WOCl₄(OPPh₃)]

Cited by 11 publications

References 21 publications

Synthesis and Reactivity of Phosphinocarbyne Complexes

Synthesis and Reactivity of Phosphinocarbyne Complexes

The reactivity of tungsten hexachloride with tetrahydrofuran and 2-methoxyethanol

Quasi-Relativistic Calculation of EPR g Tensors with Derivatives of the Decoupling Transformation, Gauge-Including Atomic Orbitals, and Magnetic Balance

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