Kinetically stabilized 1,1'-bis[(E)-dipnosphenyl]ferrocenes: syntheses, structures, properties, and reactivity

Noriyoshi Nagahora, Takahiro Sasamori, Yasuaki Watanabe, Yukio Furukawa, Norihiro Tokitoh

    Research output: Contribution to journalArticle

    29 Citations (Scopus)

    Abstract

    Kinetically stabilized 1,1'-bis[(E)-diphosphenyl]ferrocenes were synthesized by taking advantage of extremely bulky substituents, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (denoted as Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (denoted as Bbt) groups, and characterized by the spectroscopic and X-ray crystallo-graphic analyses. The electronic structures of the 1,1'-bis[(E)-diphosphenyl]ferrocenes were determined by analyzing electronic spectra, the transitions of which were reasonably assigned based on theoretical calculations. In the cyclic vol-tammograms, there were two well-defined reversible one-electron reduction couples corresponding to the intramolecular two diphosphene units. Furthermore, the 1,1'-bis[(E)-diphosphenyl]ferrocene was found to undergo ligand-exchange reactions with group 6 metal carbonyl complexes along with the E-to-Z isomerization of the diphosphene moieties, leading to the formation of the corresponding 1,1'-bis[(Z)-diphosphenyl]ferrocene group 6 metal tetracarbonyl complexes, [M(CO) 4{(Z,Z)-(BbtP=PC 5H4)2Fe}] (M = Cr, Mo, and W). The molecular structures of these complexes were determined by spectroscopic analyses ( 1H, 13C, and 31PNMR spectra, and UV-vis spectra), and that of the tungsten complex was determined by X-ray crystallographic analysis. Several types of d→ π*p=p electron transitions due to the iron and group 6 metals were detected by using UV-vis spectroscopy, and these results were supported by theoretical calculations.

    Original languageEnglish
    Pages (from-to)1884-1900
    Number of pages17
    JournalBulletin of the Chemical Society of Japan
    Volume80
    Issue number10
    DOIs
    Publication statusPublished - 2007

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    Metals
    X rays
    Tungsten
    Carbon Monoxide
    Electron transitions
    Isomerization
    Metal complexes
    Ultraviolet spectroscopy
    Molecular structure
    Electronic structure
    Iron
    Ligands
    Electrons
    ferrocene
    Bistris

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Kinetically stabilized 1,1'-bis[(E)-dipnosphenyl]ferrocenes : syntheses, structures, properties, and reactivity. / Nagahora, Noriyoshi; Sasamori, Takahiro; Watanabe, Yasuaki; Furukawa, Yukio; Tokitoh, Norihiro.

    In: Bulletin of the Chemical Society of Japan, Vol. 80, No. 10, 2007, p. 1884-1900.

    Research output: Contribution to journalArticle

    Nagahora, Noriyoshi ; Sasamori, Takahiro ; Watanabe, Yasuaki ; Furukawa, Yukio ; Tokitoh, Norihiro. / Kinetically stabilized 1,1'-bis[(E)-dipnosphenyl]ferrocenes : syntheses, structures, properties, and reactivity. In: Bulletin of the Chemical Society of Japan. 2007 ; Vol. 80, No. 10. pp. 1884-1900.
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    abstract = "Kinetically stabilized 1,1'-bis[(E)-diphosphenyl]ferrocenes were synthesized by taking advantage of extremely bulky substituents, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (denoted as Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (denoted as Bbt) groups, and characterized by the spectroscopic and X-ray crystallo-graphic analyses. The electronic structures of the 1,1'-bis[(E)-diphosphenyl]ferrocenes were determined by analyzing electronic spectra, the transitions of which were reasonably assigned based on theoretical calculations. In the cyclic vol-tammograms, there were two well-defined reversible one-electron reduction couples corresponding to the intramolecular two diphosphene units. Furthermore, the 1,1'-bis[(E)-diphosphenyl]ferrocene was found to undergo ligand-exchange reactions with group 6 metal carbonyl complexes along with the E-to-Z isomerization of the diphosphene moieties, leading to the formation of the corresponding 1,1'-bis[(Z)-diphosphenyl]ferrocene group 6 metal tetracarbonyl complexes, [M(CO) 4{(Z,Z)-(BbtP=PC 5H4)2Fe}] (M = Cr, Mo, and W). The molecular structures of these complexes were determined by spectroscopic analyses ( 1H, 13C, and 31PNMR spectra, and UV-vis spectra), and that of the tungsten complex was determined by X-ray crystallographic analysis. Several types of d→ π*p=p electron transitions due to the iron and group 6 metals were detected by using UV-vis spectroscopy, and these results were supported by theoretical calculations.",
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    AB - Kinetically stabilized 1,1'-bis[(E)-diphosphenyl]ferrocenes were synthesized by taking advantage of extremely bulky substituents, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (denoted as Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (denoted as Bbt) groups, and characterized by the spectroscopic and X-ray crystallo-graphic analyses. The electronic structures of the 1,1'-bis[(E)-diphosphenyl]ferrocenes were determined by analyzing electronic spectra, the transitions of which were reasonably assigned based on theoretical calculations. In the cyclic vol-tammograms, there were two well-defined reversible one-electron reduction couples corresponding to the intramolecular two diphosphene units. Furthermore, the 1,1'-bis[(E)-diphosphenyl]ferrocene was found to undergo ligand-exchange reactions with group 6 metal carbonyl complexes along with the E-to-Z isomerization of the diphosphene moieties, leading to the formation of the corresponding 1,1'-bis[(Z)-diphosphenyl]ferrocene group 6 metal tetracarbonyl complexes, [M(CO) 4{(Z,Z)-(BbtP=PC 5H4)2Fe}] (M = Cr, Mo, and W). The molecular structures of these complexes were determined by spectroscopic analyses ( 1H, 13C, and 31PNMR spectra, and UV-vis spectra), and that of the tungsten complex was determined by X-ray crystallographic analysis. Several types of d→ π*p=p electron transitions due to the iron and group 6 metals were detected by using UV-vis spectroscopy, and these results were supported by theoretical calculations.

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