Ferrocenyl-substituted allenylidene complexes of chromium, molybdenum and tungsten : Synthesis, structure and reactivity

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Bis(ferrocenyl)-substituted allenylidene complexes, [(CO)5MCCCFc2] (1a c, Fc = (C5H4)Fe(C5H5), M = Cr (a), Mo (b), W (c)) were obtained by sequential reaction of Fc2CO with Me3Si CCH, KF/MeOH, n-BuLi, and [(CO)5M(THF)]. For the synthesis of related mono(ferrocenyl)allenylidene chromium complexes, [(CO)5CrCCC(Fc)R] (R = Ph, NMe2), three different routes were developed: (a) reaction of the deprotonated propargylic alcohol HCCC(Fc)(Ph)OH with [(CO)5Cr(THF)] followed by desoxygenation with Cl2CO, (b) Lewis acid induced alcohol elimination from alkenyl(alkoxy)carbene complexes, [(CO)5CrC(OR)CHC(NMe2)Fc], and (c) replacement of OMe in [(CO)5CrCCC(OMe)NMe2] by Fc. Complex 1a was also formed when the mono(ferrocenyl)allenylidene complex [(CO)5CrCCC(Fc)NMe2] was treated first with Li[Fc] and the resulting adduct then with SiO2. The replacement route (c) was also applied to the synthesis of an allenylidene complex (7a) with a CC spacer in between the ferrocenyl unit and Cγ of the allenylidene ligand, [(CO)5CrCCC(NMe2)-CCFc]. The related complex containing a CHCH spacer (9a) was prepared by condensation of [(CO)5CrCCC(Me)NMe2] with formylferrocene in the presence of NEt3. The bis(ferrocenyl)-substituted allenylidene complexes 1a c added HNMe2 across the Cα Cβ bond to give alkenyl(dimethylamino)carbene complexes and reacted with diethylaminopropyne by regioselective insertion of the CC bond into the Cβ Cγ bond to afford alkenyl(diethylamino)allenylidene complexes, [(CO)5MCCC(NEt2)CMeCFc2]. The structures of 5a, 7a, and 9a were established by X-ray diffraction studies.

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540 Chemie
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Allenylidene, Ferrocene, Chromium, Molybdenum, Tungsten, Synthesis, Structure, Reactivity
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ISO 690HAAS, Thomas, Stefan OSWALD, Andrea NIEDERWIESER, Benno BILDSTEIN, Florian KESSLER, Helmut FISCHER, 2009. Ferrocenyl-substituted allenylidene complexes of chromium, molybdenum and tungsten : Synthesis, structure and reactivity. In: Inorganica Chimica Acta. 2009, 362(3), pp. 845-854. ISSN 0020-1693. Available under: doi: 10.1016/j.ica.2008.02.024
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@article{Haas2009Ferro-9878,
  year={2009},
  doi={10.1016/j.ica.2008.02.024},
  title={Ferrocenyl-substituted allenylidene complexes of chromium, molybdenum and tungsten : Synthesis, structure and reactivity},
  number={3},
  volume={362},
  issn={0020-1693},
  journal={Inorganica Chimica Acta},
  pages={845--854},
  author={Haas, Thomas and Oswald, Stefan and Niederwieser, Andrea and Bildstein, Benno and Kessler, Florian and Fischer, Helmut}
}
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