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A series of enantiomerically pure −SiMe2NR2 (R = Me, Et) substituted pentadienyl ligands were prepared starting from the natural product (1R)-(−)-myrtenal. Deprotonation with a Schlosser superbase yields the corresponding potassium salts, which were characterized by various spectroscopic techniques. In solution these neutral N-donor-substituted pentadienyl systems predominantly adopt a U conformation, but in two cases the rare S conformation was also observed as a minor component in solution. Addition of 18-crown-6 allowed the molecular structures of two of these potassium pentadienyls to be determined by X-ray diffraction. Interestingly, η5 and κN coordination of the pentadienyl system to the [K(18-crown-6)]+ cation was observed. Furthermore, these ligand systems also coordinate to transition metals and form an open titanocene, open vanadocenes, open chromocenes, and half-open trozircenes with [TiCl3(thf)3], [VCl3(thf)3], CrCl2, and [(η7-C7H7)ZrCl(tmeda)], respectively. These complexes were characterized...

Bulky pyrrolyl ligands have been used for the synthesis of diazaferrocenes, which have been characterized by various spectroscopic techniques, including X-ray diffraction for rac-[{η5-2,3,5-(Me3C)3...