Selective oxidants for organometallic compounds containing a stabilising anion of highly reactive cations: (3,5(CF3)2C6H3)4B−)Cp2Fe+ and (3,5(CF3)2C6H3)4B−)Cp*2Fe+

Chávez, Ivonne; Alvarez-Carena, Angel; Molins, Elı́es; Roig, Anna; Maniukiewicz, Waldemar; Arancibia, Alenjandra; Arancibia, Veróníca; Brand, Holger; Manríquez, J.

doi:10.1016/s0022-328x(00)00044-9

Cited by 79 publications

(92 citation statements)

References 25 publications

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“…1). The eclipsed conformation of the Cp rings has been observed in the trigonal structure of [Fe(C 5 H 5 ) 2 ][AsF 6 ] [7] while the staggered form is seen in [Fe (C 5 [9] and the monoclinic structure of [Fe(C 5 H 5 ) 2 ][AsF 6 ] [7] The average Fe-C distance in 2 is 0.005 A longer than the corresponding distance in ferrocene while the Fe-centroid distance is 0.035 A longer [10]; these distances are similar to other ferrocenium salts [8,11] (Table 2). Intermolecular interactions similar to those associated with weak hydrogen bonding were noted between the hydrogen atoms and adjacent fluorine atoms ( .…”

Section: Resultsmentioning

confidence: 99%

Synthesis and reactivity of [N(C6H4Br)3][B(C6F5)4]: the X-ray crystal structure of [Fe(C5H5)2][B(C6F5)4]

O’Connor¹,

Nataro²,

Golen³

et al. 2004

Journal of Organometallic Chemistry

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Section: Resultsmentioning

confidence: 99%

Synthesis and reactivity of [N(C6H4Br)3][B(C6F5)4]: the X-ray crystal structure of [Fe(C5H5)2][B(C6F5)4]

O’Connor¹,

Nataro²,

Golen³

et al. 2004

Journal of Organometallic Chemistry

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“…Dry solvents were prepared by distillation from the appropriate drying agent prior to use as follows: CH 2 Cl 2 (CaH 2 ), ClCH 2 CH 2 Cl (CaCl 2 ), CH 3 CN (CaH 2 ), benzene (Na), THF (Na-benzophenone), and DMF (CaH 2 ). 2-Ruthenocenyl-1,3-dioxaborolane (1), [14] 1,4-bis(ruthenocenyl)buta-1,3-diyne, [19] 1,4-bis(1ЈЈ,2ЈЈ,3ЈЈ,4ЈЈ,5ЈЈ-pentamethylruthenocenyl)buta-1,3-diyne, [13] 1,8-bis(1ЈЈ,2ЈЈ,3ЈЈ,4ЈЈ,5ЈЈ-pentamethylruthenocenyl)octa-1,3,5,7-tetrayne, [13] thieno [3,2-b]thiophene, [20] 3,6-dimethylthieno[3,2-b]-thiophene, [21] 2,5-diiodo-3,4-ethylenedioxythiophene, [22] dichloro-[1,1Ј-bis(diphenylphosphanyl)ferrocene]palladium, (dppf)PdCl 2 , [23] and ferricenium tetra{3,5-bis(trifluoromethyl)phenyl}borate [24] were prepared according to the literature procedures. Other reagents were used as received from commercial suppliers.…”

Section: Discussionmentioning

confidence: 99%

Synthesis and Some Properties of Bis(ruthenocenyl)thiophene Derivatives – Possible Spin‐Coupling in the Two‐Electron Oxidized Species of Dinuclear Ruthenocenes Bridged by Thiophene Derivatives

et al. 2006

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The binuclear ruthenocene derivatives bridged by thiophene, 3,4-ethylenedioxythiophene, 2,2Ј-bithiophene, thieno[3,2-b]thiophene, or 3,6-dimethylthieno[3,2-b]thiophene were prepared by the Suzuki coupling of 2-ruthenocenyl-4,5-tetramethyl-1,3-dioxaborolane with the corresponding diiodo compounds. In addition, thiophene-and bithiophenebridged binuclear pentamethylruthenocenes were prepared by the reaction of bis(pentamethylruthenocenyl)diyne and -tetrayne with NaSH, respectively. The cyclic voltammograms of these complexes exhibit one-step two-electron redox waves in the lower potential region (0-0.3 V versus FcH/ FcH + ). The two-electron oxidized species of the thiophene-

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“…Unless noted, chemicals were purchased from commercial sources and used without further purification. KC 8 , 35 (dmp)N 3 , 15 [Cp 2 Fe][B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 ], 36 and [(dtbpe)Ni] 2 (C 6 H 6 ) 37 were prepared according to the literature methods. All NMR spectra were recorded using a Bruker DRX-400 or DRX-500 spectrometer.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Characterization of Three-Coordinate Ni(III)-Imide Complexes

et al. 2011

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A new family of low-coordinate nickel imides supported by 1,2-bis(di-tert-butylphosphino)ethane was synthesized. The oxidation of nickel(II) complexes led to the formation of both aryl- and alkyl-substituted nickel(III) imides, and examples of both types have been isolated and fully characterized. The aryl substituent that proved most useful in stabilizing the Ni(III)-imide moiety was the bulky 2,6-dimesitylphenyl. The two nickel(III)-imide compounds showed different variable-temperature magnetic properties, but analogous EPR spectra at low temperatures. In order to account for this discrepancy, a low-spin/high-spin equilibrium was proposed to take place for the alkyl-substituted imide nickel(III) complex. This proposal was supported by DFT calculations. DFT calculations also indicated that the unpaired electron is mostly localized on the imide nitrogen for the nickel(III) complexes. The results of reactions carried out in the presence of hydrogen donors supported the findings from DFT calculations that the adamantyl substituent was a significantly more reactive hydrogen-atom abstractor. Interestingly, the steric properties of the 2,6-dimesitylphenyl substituent are important not only in protecting the Ni=N core but also in favoring one rotamer of the resulting nickel(III) imide, by locking in the phenyl ring in a perpendicular orientation with respect to the NiPP plane.

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Selective oxidants for organometallic compounds containing a stabilising anion of highly reactive cations: (3,5(CF3)2C6H3)4B−)Cp2Fe+ and (3,5(CF3)2C6H3)4B−)Cp*2Fe+

Cited by 79 publications

References 25 publications

Synthesis and reactivity of [N(C6H4Br)3][B(C6F5)4]: the X-ray crystal structure of [Fe(C5H5)2][B(C6F5)4]

Synthesis and reactivity of [N(C6H4Br)3][B(C6F5)4]: the X-ray crystal structure of [Fe(C5H5)2][B(C6F5)4]

Synthesis and Some Properties of Bis(ruthenocenyl)thiophene Derivatives – Possible Spin‐Coupling in the Two‐Electron Oxidized Species of Dinuclear Ruthenocenes Bridged by Thiophene Derivatives

Synthesis and Characterization of Three-Coordinate Ni(III)-Imide Complexes

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