Indirect and Direct Grafting of Transition Metals to Siliconoids.

Authors :: Poitiers NE
Giarrana L
Leszczyńska KI
Huch V
Zimmer M
Scheschkewitz D
Source :: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2020 May 25; Vol. 59 (22), pp. 8532-8536. Date of Electronic Publication: 2020 Mar 20.
Publication Year :: 2020
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 <subscript>6</subscript> siliconoid (1Li) and Cp <subscript>2</subscript> MCl <subscript>2</subscript> (M=Zr, Hf). Charge-neutral siliconoid ligands with pending tetrylene functionality were prepared by the reaction of amidinato chloro tetrylenes [PhC(NtBu) <subscript>2</subscript> ]ECl (E=Si, Ge, Sn) with 1Li, thus confirming the principal compatibility of such low-valent functionalities with the unsaturated Si <subscript>6</subscript> cluster scaffold. The pronounced donor properties of the tetrylene/siliconoid hybrids allow for their coordination to the Fe(CO) <subscript>4</subscript> fragment.<br /> (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)