The structure of μ-(η-cyclopentadienyl)-bis[(η-cyclopentadienyl)nickel(III)] tetrafluoroborate at 190 and 295 K

Dubler, E.; Textor, Marcus; Oswald, H. R.; Jameson, Geoffrey B.

doi:10.1107/s0108768183003055

Cited by 36 publications

(10 citation statements)

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“…In addition, the C–C bonds within the bridging Cp′ ring (average 1.462 Å) are significantly longer than those in free Cp′ 2 Fe (1.422 Å) but close to those in Cp* 2 Fe (1.461 Å). To the extent that bond length can be correlated with bond strength, these data suggest weaker Fe–C and C–C interactions for the bifacially coordinated bridging ring in comparison with the singly coordinated terminal rings. , …”

Section: Resultssupporting

confidence: 83%

“…27 To the extent that bond length can be correlated with bond strength, these data suggest weaker Fe−C and C−C interactions for the bifacially coordinated bridging ring in comparison with the singly coordinated terminal rings. 30,31 Mossbauer effect (ME) spectroscopy of 1•BF 4 accumulated over the temperature interval 90 < T < 273 K evidenced the expected doublet spectra for diamagnetic Fe(II), and a typical spectrum is shown in Figure 2.…”

Section: ■ Introductionmentioning

confidence: 99%

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Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene

et al. 2015

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Three new triple-decker complexes were synthesized by the reaction of nonamethylferrocene, Cp′FeCp* (Cp′ = C5Me4H, Cp* = C5Me5), with coordinatively unsaturated transition-metal complexes. The reaction of ruthenium cations [(C5R5)Ru]+ (R = H, Me) with Cp′FeCp* afforded the purple heterometallic triple-decker complexes [(C5R5)Ru(μ-Cp′)FeCp*]+ by electrophilic addition of ruthenium to the Cp′ ring of nonamethylferrocene. The analogous reaction with the manganese cation [Mn(CO)3]+ produced the blue homometallic triple-decker complex [Cp*Fe(μ-Cp′)FeCp*]+ by abstraction of the Cp′ ring from Cp′FeCp* and subsequent addition of the newly generated cation [Cp*Fe]+ to 1 equiv of Cp′FeCp*. These experiments demonstrate that the asymmetry of Cp′FeCp* gives rise to a remarkable degree of regioselectivity such that ruthenium electrophiles add only to the Cp′ ring and never to the Cp* ring. In a similar way, [Mn(CO)3]+ abstracts only the Cp′ ring from Cp′FeCp* to produce [Cp*Fe]+, which in turn adds only to the Cp′ ring of Cp′FeCp* to produce [Cp*Fe(μ-Cp′)FeCp*]+. Three air-stable triple-decker complexes incorporating nonamethylferrocene, [Cp*Fe(μ-Cp′)FeCp*]+ (1), [CpRu(μ-Cp′)FeCp*]+ (2), and [Cp*Ru(μ-Cp′)FeCp*]+ (3), have been characterized by NMR spectroscopy, elemental analysis, single-crystal X-ray diffraction analysis, and temperature-dependent 57Fe Mössbauer spectroscopy.

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Section: Resultssupporting

confidence: 83%

Section: ■ Introductionmentioning

confidence: 99%

Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene

et al. 2015

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“…The C-C bond distances range from 1.38 to I . 53 A in the cp, ring and from 1.22 to 1.48 8, in cp,, and are similar to those found for [Nio(q-C,H,)(C,Ph,)]56 (1.24- clearly indicate that the Co(q-C,H,), entity in this compound is present as the cobaltocenium cation [Co(q-C,H,),]+.…”

Section: [Co(~-cshs)~i "I(c3sandi 3*2mecnmentioning

confidence: 99%

Synthesis, structure and characterization of mixed cyclopentadienyl–dithiolene metal complexes, [Co(η-C₅H₅)₂][Ni(C₃S₅)₂]₃·2MeCN and [Ni(η-C₅H₅)(C₃S₅)]

Faulmann¹,

Delpech²,

Malfant³

et al. 1996

J. Chem. Soc., Dalton Trans.

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Two new compounds [Co(q-C,H,),][Ni(C3S,),I,.2MeCN and [Ni(q-C,H,)(C,S,)], both obtained by combination of the nickel complex anion [Ni(C,S,),] -(C,S, = 4,5-disulfanyl-l,3-dithiole-2-thionate) and the metallocenium cation [M(q-C5H,),] + (M = Co or Ni), respectively, have been prepared and characterized crystallographically. The non-integral oxidation-state cobalt complex with the unusual 1 : 3 stoichiometry was obtained by electrochemical oxidation of [NBu,][Ni(C,S,),] in the presence of [Co(q-C,H,),]PF,. It is semiconductive (0 = 0.06 S cm ' at room temperature, E, = 0.18 eV between 300 and 250 K). The crystal structure shows that the asymmetric unit contains one Ni(C,S,), unit, one Ni(C,S,) entity, one Co (q-C,H,) unit and one molecule of acetonitrile. The Ni(C,S,), units are associated in triads stacked along the [ l o l l direction. No significant differences are observed in the distances and angles within the two symmetryunrelated Ni(C,S,), units, indicating that the charges of both units are very similar. The cyclopentadienyl rings are staggered due to the location of the Co atoms on inversion centres. The average Co-C distance is comparable to those found in several cobaltocenium salts.

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“…(Dubler et al 1983). It is, however, notable that the average atomic location thermal coefficient for simple inorganic crystals is about 10-3 A K -I, with variations generally less than one additional order of magnitude; since r is of the order of 1 A, dr/rdT is about 10-3 K-1 .…”

Section: Atomic Location Thermal Dependencementioning

confidence: 99%

Atomic Contribution to Crystalline Property Temperature Dependence

Abrahams¹

1985

Aust. J. Phys.

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Aust. J. Phys., 1985, 38, 289-98 General atomic locations in crystal structures are temperature dependent: the average thermal change in simple inorganic crystals is of the order of 10 -3 A K -1, with corresponding thermal coefficients of about 10 -3 K -1. A survey of the thermal coefficients for seven important crystal properties shows that these also have average values of about 10 -3 K -1, within one order of magnitude. Correlations between microscopic and macroscopic thermal dependence have been developed for the properties of spontaneous polarization and spontaneous strain. Comparable correlations are predicted for the case of piezoelectric strain. Scaling considerations suggest that the remaining dielectric, thermal and optical properties are similarly related to atomic location thermal coefficients. By contrast, the much smaller thermal dependence of such properties as expansivity and refractive index, with coefficients of about 10 -5 K -1, suggests that these properties are dominated by electronic rather than ionic interactions.

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The structure of μ-(η-cyclopentadienyl)-bis[(η-cyclopentadienyl)nickel(III)] tetrafluoroborate at 190 and 295 K

Abstract: The structure of [Ni2 (

Cited by 36 publications

References 20 publications

Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene

Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene

Synthesis, structure and characterization of mixed cyclopentadienyl–dithiolene metal complexes, [Co(η-C₅H₅)₂][Ni(C₃S₅)₂]₃·2MeCN and [Ni(η-C₅H₅)(C₃S₅)]

Atomic Contribution to Crystalline Property Temperature Dependence

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The structure of μ-(η-cyclopentadienyl)-bis[(η-cyclopentadienyl)nickel(III)] tetrafluoroborate at 190 and 295 K

Abstract: The structure of [Ni2 (

Cited by 36 publications

References 20 publications

Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene

Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene

Synthesis, structure and characterization of mixed cyclopentadienyl–dithiolene metal complexes, [Co(η-C5H5)2][Ni(C3S5)2]3·2MeCN and [Ni(η-C5H5)(C3S5)]

Atomic Contribution to Crystalline Property Temperature Dependence

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Synthesis, structure and characterization of mixed cyclopentadienyl–dithiolene metal complexes, [Co(η-C₅H₅)₂][Ni(C₃S₅)₂]₃·2MeCN and [Ni(η-C₅H₅)(C₃S₅)]