Abstract
Unsaturated charge-neutral silicon clusters (siliconoids) are important as gas-phase intermediates between molecules and the elemental bulk. With stable zirconocene- and hafnocene-substituted derivatives, we here report the first examples containing directly bonded transition-metal fragments that are readily accessible from the ligato-lithiated Si(6) siliconoid (1Li) and Cp(2) MCl(2) (M=Zr, Hf). Charge-neutral siliconoid ligands with pending tetrylene functionality were prepared by the reaction of amidinato chloro tetrylenes [PhC(NtBu)(2) ]ECl (E=Si, Ge, Sn) with 1Li, thus confirming the principal compatibility of such low-valent functionalities with the unsaturated Si(6) cluster scaffold. The pronounced donor properties of the tetrylene/siliconoid hybrids allow for their coordination to the Fe(CO)(4) fragment.