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

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

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30 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 Dec 1

ASJC Scopus subject areas

  • Chemistry(all)

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