Structures of two gold(I) complexes with tricyclohexylphosphine: [(Cy3P)AuCl] and [(Cy3P)2Au]+.Cl−

Muir, James A.; Muir, Mariel M.; Pulgar, Lillian Bird; Jones, Peter G.; Sheldrick, George M.

doi:10.1107/s010827018500703x

Cited by 36 publications

(23 citation statements)

References 9 publications

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“…For further comparisons between B3LYP, TPSS and M05 functionals, we next examine the correlations between optimized structures of ClAu(PR3) and the reported X-ray crystal structures ( Figure 2). [28][29][30][31][32][33][34][35][36] According to Figure 2, the calculation results with all functionals show good agreement with the reported X-ray crystal structures, whereas the Au-Cl and Au-P bond distances of all ClAu(PR 3 ) complexes are slightly overestimated (relative to the experimental ones). The reason might be attributed to that the use of ECP slightly underestimated the electrophilicity of Au atom.…”

Section: Resultssupporting

confidence: 83%

Accurate Prediction of AuP Bond Strengths by Density Functional Theory Methods

Liu

Dang

et al. 2012

Chin. J. Chem.

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The recent development of Au‐catalyzed reactions has greatly enriched the methods of organic synthesis. The phosphine or phosphate‐coordinated Au complexes have shown high efficiency in catalyzing various CC and CH activations. In many of these reactions, the AuP bond strength was found to play an important role in determining the catalytic efficiency. In the present study, the accuracy of different theoretical methods for prediction of AuP strengths has been examined on basis of the experimental enthalpy changes between different ClAu(PR3) and ClAu(THT) (THT=tetrahydrothiophene). By comparing the different DFT functionals (e.g. B3LYP, TPSS, M06), different basis sets (including the different effective core potentials on Au and the total electron basis sets on all other atoms), and different solution phase single point calculations, we found that the TPSS/(CPE‐121G+f:6‐311+G(d,p)(SMD)//TPSS/(CPE‐121G:6‐31G(d) (M1) method gives the best correlations with the available experimental results. Meanwhile, the calculations with B3LYP//TPSS and M05//TPSS also give comparable calculation results. Finally, the specified method (M1) is used to calculate the AuP bond dissociation enthalpies and energies of different ClAu(PR3)/ClAu(P(OR)3) complexes. By accurately reproducing the available experimental results, we believe that the method (M1) is reliable for the theoretical analysis of Au‐P systems.

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Section: Resultssupporting

confidence: 83%

Accurate Prediction of AuP Bond Strengths by Density Functional Theory Methods

Liu

Dang

et al. 2012

Chin. J. Chem.

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“…The geometry around the gold atom is almost perfectly linear with a P-Au-P angle of 178.16 (8) . [15,16] The sulfur atoms are located at 3.786 and 3.747 from the gold atom but this distance is too long to consider any bonding interaction. [15,16] The sulfur atoms are located at 3.786 and 3.747 from the gold atom but this distance is too long to consider any bonding interaction.…”

Section: Resultsmentioning

confidence: 99%

Heteropolynuclear Complexes with the Ligand Ph2PCH2SPh: Theoretical Evidence for Metallophilic Au−M Attractions

et al. 2000

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“…In both complexes, the coinage metal atom is in a linear [ 4 : 176.64(2)°, 5 : 172.29(2)°] coordination environment. As a result of the electron‐rich character of 3 the Au−Cl bond length in 4 [2.3415(6) Å] is significantly longer than that of [AuCl(PCy 3 )] [2.279(5) Å] . The average P−N distances in 4 [1.641(2) Å] and 5 [1.649(2) Å] are shorter than that of the free phosphine 3 [1.689(2) Å], indicating a more pronounced N to P hyperconjugation upon complexation of the coinage metal ions.…”

Section: Figurementioning

confidence: 99%

Tris(imidazolin‐2‐ylidenamino)phosphine: A Crystalline Phosphorus(III) Superbase That Splits Carbon Dioxide

Mehlmann

Mück‐Lichtenfeld

Tan

et al. 2016

Chemistry A European J

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We report the synthesis and remarkable properties of the phosphine P(NIiPr) (NIiPr=1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidenamino), a crystalline solid accessible through a short and scalable route. Evaluation of the electron-donor properties reveals a Tolman electronic parameter (TEP) value of 2029.7 cm for the new phosphine that is significantly lower than those of all known phosphines or even N-heterocyclic carbenes. Moreover, P(NIiPr) is more basic [pK (MeCN)=38.8] than Verkade's proazaphosphatranes, thus being the strongest reported nonionic phosphorus(III) superbase. The coordination chemistry of the new phosphine towards different metal centers has been explored, and due to its unique electron-releasing character, the phosphine is capable of capturing and cleaving the CO molecule.

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Structures of two gold(I) complexes with tricyclohexylphosphine: [(Cy3P)AuCl] and [(Cy3P)2Au]+.Cl−

Cited by 36 publications

References 9 publications

Accurate Prediction of AuP Bond Strengths by Density Functional Theory Methods

Accurate Prediction of AuP Bond Strengths by Density Functional Theory Methods

Heteropolynuclear Complexes with the Ligand Ph2PCH2SPh: Theoretical Evidence for Metallophilic Au−M Attractions

Tris(imidazolin‐2‐ylidenamino)phosphine: A Crystalline Phosphorus(III) Superbase That Splits Carbon Dioxide

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