The crystal and molecular structure of Zeise's salt, KPtCl3.C2H4.H2O

Black, M.E.; Mais, R. H. B.; Owston, P. G.

doi:10.1107/s0567740869004699

Cited by 82 publications

(48 citation statements)

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“…These results are similar to those found in the anion in Zeise's salt (Black, Mais & Owston, 1969;Hamilton, 1969), and in other platinum(II)-olefin 1r-complexes (Alderman, Owston & Rowe, 1960;Mason & Robertson, 1969;Spagna et al, 1970a, b).…”

Section: Anionsupporting

confidence: 86%

The crystal structure of tetraphenylphosphonium trichloro-(cis-but-2-en-1,4-diol)platinum(II)

Colapietro¹,

Zambonelli²

1971

Acta Crystallogr B Struct Sci

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Section: Anionsupporting

confidence: 86%

The crystal structure of tetraphenylphosphonium trichloro-(cis-but-2-en-1,4-diol)platinum(II)

Colapietro¹,

Zambonelli²

1971

Acta Crystallogr B Struct Sci

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“…The ethylene moiety should also become non-planar. X-ray [4] and neutron [5,6] diffraction measurements have shown that the C@C bond distance is indeed increased by 0.038 Å over the value for free ethylene. Platinum-alkene complexes have also been investigated by vibrational spectroscopy, where it would be expected that a weakening of the C@C bond would result in a lowering of the C@C force constant and, therefore, a reduction in the associated vibrational frequency.…”

Section: Introductionmentioning

confidence: 92%

Effect of high external pressures on the vibrational spectra of Zeise’s complexes, K[Pt(η2-C2H4)Cl3] and [Pt(η2-C2H4)Cl2]2

Baldwin¹,

Gilson²,

Butler³

2005

Journal of Organometallic Chemistry

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“…[1][2][3][4] Such transition metalolefin complexes are best understood by the Dewar-ChattDuncanson (DCD) model, [5,6] which introduced the concept of ligand to metal s-donation and metal to ligand p-back donation. [7] Accordingly alkene (and alkyne) complexes were investigated in detail by experimental [8][9][10][11] as well as theoretical [12][13][14][15] methods.…”

Section: Introductionmentioning

confidence: 99%

Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)

Reisinger

Trapp

Knapp

et al. 2009

Chemistry A European J

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Compounds including the free or coordinated gas-phase cations [Ag(eta(2)-C(2)H(4))(n)](+) (n = 1-3) were stabilized with very weakly coordinating anions [A](-) (A = Al{OC(CH(3))(CF(3))(2)}(4), n = 1 (1); Al{OC(H)(CF(3))(2)}(4), n = 2 (3); Al{OC(CF(3))(3)}(4), n = 3 (5); {(F(3)C)(3)CO}(3)Al-F-Al{OC(CF(3))(3)}(3), n = 3 (6)). They were prepared by reaction of the respective silver(I) salts with stoichiometric amounts of ethene in CH(2)Cl(2) solution. As a reference we also prepared the isobutene complex [(Me(2)C=CH(2))Ag(Al{OC(CH(3))(CF(3))(2)}(4))] (2). The compounds were characterized by multinuclear solution-NMR, solid-state MAS-NMR, IR and Raman spectroscopy as well as by their single crystal X-ray structures. MAS-NMR spectroscopy shows that the [Ag(eta(2)-C(2)H(4))(3)](+) cation in its [Al{OC(CF(3))(3)}(4)](-) salt exhibits time-averaged D(3h)-symmetry and freely rotates around its principal z-axis in the solid state. All routine X-ray structures (2theta(max.) < 55 degrees) converged within the 3sigma limit at C=C double bond lengths that were shorter or similar to that of free ethene. In contrast, the respective Raman active C=C stretching modes indicated red-shifts of 38 to 45 cm(-1), suggesting a slight C=C bond elongation. This mismatch is owed to residual librational motion at 100 K, the temperature of the data collection, as well as the lack of high angular data owing to the anisotropic electron distribution in the ethene molecule. Therefore, a method for the extraction of the C=C distance in [M(C(2)H(4))] complexes from experimental Raman data was developed and meaningful C=C distances were obtained. These spectroscopic C=C distances compare well to newly collected X-ray data obtained at high resolution (2theta(max.) = 100 degrees) and low temperature (100 K). To complement the experimental data as well as to obtain further insight into bond formation, the complexes with up to three ligands were studied theoretically. The calculations were performed with DFT (BP86/TZVPP, PBE0/TZVPP), MP2/TZVPP and partly CCSD(T)/AUG-cc-pVTZ methods. In most cases several isomers were considered. Additionally, [M(C(2)H(4))(3)] (M = Cu(+), Ag(+), Au(+), Ni(0), Pd(0), Pt(0), Na(+)) were investigated with AIM theory to substantiate the preference for a planar conformation and to estimate the importance of sigma donation and pi back donation. Comparing the group 10 and 11 analogues, we find that the lack of pi back bonding in the group 11 cations is almost compensated by increased sigma donation.

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The crystal and molecular structure of Zeise's salt, KPtCl₃.C₂H₄.H₂O

Cited by 82 publications

References 1 publication

The crystal structure of tetraphenylphosphonium trichloro-(cis-but-2-en-1,4-diol)platinum(II)

The crystal structure of tetraphenylphosphonium trichloro-(cis-but-2-en-1,4-diol)platinum(II)

Effect of high external pressures on the vibrational spectra of Zeise’s complexes, K[Pt(η2-C2H4)Cl3] and [Pt(η2-C2H4)Cl2]2

Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)

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The crystal and molecular structure of Zeise's salt, KPtCl3.C2H4.H2O

Cited by 82 publications

References 1 publication

The crystal structure of tetraphenylphosphonium trichloro-(cis-but-2-en-1,4-diol)platinum(II)

The crystal structure of tetraphenylphosphonium trichloro-(cis-but-2-en-1,4-diol)platinum(II)

Effect of high external pressures on the vibrational spectra of Zeise’s complexes, K[Pt(η2-C2H4)Cl3] and [Pt(η2-C2H4)Cl2]2

Silver–Ethene Complexes [Ag(η2‐C2H4)n][Al(ORF)4] with n=1, 2, 3 (RF=Fluorine‐Substituted Group)

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The crystal and molecular structure of Zeise's salt, KPtCl₃.C₂H₄.H₂O

Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)