The dichloromethane induced fragmentation of ferrocenylmethyldimethylamine. Mechanistic aspects and crystallographic and electrochemical investigation of the (FcCH2)2NMe2+ and FcCH2NMe2H+ ions1

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1998
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Wolmershäuser, Gotthelf
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Journal of Organometallic Chemistry. 1998, 570(2), pp. 201-218. ISSN 0022-328X. Available under: doi: 10.1016/S0022-328X(98)00866-3
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Ferrocenylmethyldimethylamine, FcCH2NMe2, reacts with CH2Cl2 in either the presence or absence of non-coordinating counterions to give equimolar amounts of the bis(ferrocenylmethyl)dimethyl ammonium salts (FcCH2)2NMe2+X− (X−=PF6−, SbF6−, BPh4− or Cl−, 1a–d) and the corresponding protonated ammonium salts FcCH2NMe2H+ which have been isolated as the SbF6− and Cl− salts 2b,d. The reaction proceeds via fragmentation of an intermediate quaternary chloromethylated ammonium ion to chloromethylferrocene, FcCH2Cl, and dimethyliminium chloride NMe2CH2+Cl−. The parent amine acts as a nucleophile toward FcCH2Cl to give 1a–d and as a base toward NMe2CH2+ to give FcCH2NMe2H+, NMe2H and (Me2N)2CH2. The FcCH2Cl intermediate is intercepted by NEt3 while KCN or LiH do not successfully compete with FcCH2NMe2. A new, non-toxic, selective, high-yield route to 1d is also presented. Electrochemistry and UV–vis spectroelectrochemistry reveal, that the two identical redox centers in 1a–d are essentially non-interacting. Individual E1/2 values have been determined for different solvents by digital simulation. The corresponding ferrocenium salts were prepared by either chemical or electrochemical means and accordingly characterized. Our studies are augmented by X-ray structure analyses of 1b, 1d and 2d. 1d contains three different cation conformers and four molecules of water per unit cell. The latter are hydrogen bonded to the chloride counterions to form one-dimensional infinite chains parallel to the a axis.

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ISO 690WINTER, Rainer F., Gotthelf WOLMERSHÄUSER, 1998. The dichloromethane induced fragmentation of ferrocenylmethyldimethylamine. Mechanistic aspects and crystallographic and electrochemical investigation of the (FcCH2)2NMe2+ and FcCH2NMe2H+ ions1. In: Journal of Organometallic Chemistry. 1998, 570(2), pp. 201-218. ISSN 0022-328X. Available under: doi: 10.1016/S0022-328X(98)00866-3
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@article{Winter1998dichl-13859,
  year={1998},
  doi={10.1016/S0022-328X(98)00866-3},
  title={The dichloromethane induced fragmentation of ferrocenylmethyldimethylamine. Mechanistic aspects and crystallographic and electrochemical investigation of the (FcCH2)2NMe2+ and FcCH2NMe2H+ ions1},
  number={2},
  volume={570},
  issn={0022-328X},
  journal={Journal of Organometallic Chemistry},
  pages={201--218},
  author={Winter, Rainer F. and Wolmershäuser, Gotthelf}
}
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