Metal-Olefin Compounds. VIII. The Crystal Structure of a Norbornadiene-Silver Nitrate Complex, C7H8.2AgNO3

Baenziger, N. C.; Haight, H. L.; Alexander, Rikki; Doyle, Joseph

doi:10.1021/ic50042a025

Cited by 41 publications

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“…These compounds are complexes of [Ag][A] (e.g. : A = BF 4 , ClO 4 , SO 3 CF 3 ) with chelating ligands such as 1,5-hexadiene, [28] norbornadiene, [22] 1,4,7-cyclononatriene, [23] 1,3,5,7-cyclooctatetraene (and derivatives), [20,24,25,50,51] bullvalene, [26] tetraphenylethene, -butadiene [19] and other substituted alkenes. [17,18,21,27,52] However, these olefins are solids or liquids and, therefore, the entropic contribution to dissociation (and thus decomposition) is much smaller than that for the lightest parent olefin C 2 H 4 .…”

Section: -C H 4 ) 3 ]mentioning

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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Section: -C H 4 ) 3 ]mentioning

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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“…It is well known that silver forms complexes with unsaturated groups, present either as olefins or as aromatic rings [1][2][3][4][5][6][7][8][9][10][11][12]. Many of these tend to be unstable solids or transient species within polymer membranes used as olefin separation devices.…”

Section: Introductionmentioning

confidence: 99%

The first chelating olefin: Solid-state structure of bis-(η1-4-phenyl-η2-1-butene)silver (I) tetrafluoroborate

Whitcomb¹,

Rajeswaran²

2007

Journal of Organometallic Chemistry

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“…The differing stoichiometry of the complexes of norbornadiene with AgBF4 and AgN03 (1-4) is probably due to the differing coordination of the silver ion with the respective anion, as has been suggested earlier for 1,3-butadiene (6). The structural investigation of Baenziger et al (5) has established a bonding between the silver ion and the nitrate ion in 2AgNO 3.C7Hs.…”

Section: Discussionmentioning

confidence: 67%

Coordination compounds of norbornadiene with silver tetrafluoroborate

Quinn¹

1968

Can. J. Chem.

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Crystalline complexes of norbornadiene with silver tetrafluoroborate have been obtained both from anhydrous and aqueous solution. While both solutions yield complexes of stoichiometry AgBF4•C7H8 and 2AgBF4•3C7H8, those from the aqueous solutions also contain water of crystallization. The infrared spectra show that norbornadiene is similarly complexed in both the anhydrous and hydrated complexes but that the coordination in the 1:1 complex is different from that in the 2:3 complex. The anhydrous and hydrated 1:1 complexes have the same X-ray diffraction powder patterns while those of 2:3 complexes are different.

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Metal-Olefin Compounds. VIII. The Crystal Structure of a Norbornadiene-Silver Nitrate Complex, C₇H₈.2AgNO₃

Cited by 41 publications

References 0 publications

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

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

The first chelating olefin: Solid-state structure of bis-(η1-4-phenyl-η2-1-butene)silver (I) tetrafluoroborate

Coordination compounds of norbornadiene with silver tetrafluoroborate

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Metal-Olefin Compounds. VIII. The Crystal Structure of a Norbornadiene-Silver Nitrate Complex, C7H8.2AgNO3

Cited by 41 publications

References 0 publications

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

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

The first chelating olefin: Solid-state structure of bis-(η1-4-phenyl-η2-1-butene)silver (I) tetrafluoroborate

Coordination compounds of norbornadiene with silver tetrafluoroborate

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Metal-Olefin Compounds. VIII. The Crystal Structure of a Norbornadiene-Silver Nitrate Complex, C₇H₈.2AgNO₃

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

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