Syntheses, structures and electrochemistry of some 1-(η²-allylamino)-1-ferrocenylcarbene complexes of chromium(0), molybdenum(0) and tungsten(0). Part 13. The chemistry of metallacyclic alkenylcarbene complexes

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Schobert, Rainer ; Kempe, Rhett ; Schmalz, Thomas ; Gmeiner, Alexander:
Syntheses, structures and electrochemistry of some 1-(η²-allylamino)-1-ferrocenylcarbene complexes of chromium(0), molybdenum(0) and tungsten(0). Part 13. The chemistry of metallacyclic alkenylcarbene complexes.
In: Journal of Organometallic Chemistry. Bd. 691 (2006) Heft 5 . - S. 859-868.
ISSN 1872-8561
DOI: https://doi.org/10.1016/j.jorganchem.2005.10.047

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Abstract

The metallacyclic complexes (OC)4MC(η2-NHCH2CHCHX)Fc (4; X=H) and (5; X=CH2OH) M=Cr: a; Mo: b; W: c; Fc=ferrocenyl=CpFe(C5H4) were obtained in good yields upon photo-decarbonylation of the bimetallic allylaminocarbene complexes (OC)5MC(NHCH2CHCHX)Fc (2; X=H)/(3; X=CH2OH). At room temperature complexes 2/3 exist as mixtures of E- and predominantly Z-isomers with regard to the C–N bond. The molecular structures of 4b and 4c were determined by X-ray diffraction analyses. The intermetallic communicative effects and the interplay of Fc and η2-alkene moieties of 4a and 4b were assessed by cyclovoltammetry. All complexes were also characterized in solution by one- and two-dimensional NMR spectroscopy (1H, 13C, 1H NOE, 1H/1H COSY, 13C/1H HETCOR).