Controlled cluster expansion at a Zintl cluster surface.

Authors :: Townrow OPE
Weller AS
Goicoechea JM
Source :: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Jan 15; Vol. 63 (3), pp. e202316120. Date of Electronic Publication: 2023 Dec 14.
Publication Year :: 2024
Abstract: Reaction of the tris-hypersilyl nonagermanide Zintl cluster salt, K[Ge <subscript>9</subscript> (Hyp) <subscript>3</subscript> ] (Hyp=Si(SiMe <subscript>3</subscript> ) <subscript>3</subscript> ) with [Rh(η <superscript>2</superscript> ,η <superscript>2</superscript> -L)Cl] <subscript>2</subscript> (L=1,5-cyclooctadiene, COD; norbornadiene, NBD) afforded eleven- and twelve-vertex homo-multimetallic clusters by cluster core expansion. Using a stepwise procedure, starting from the Zintl cluster [Rh(COD){Ge <subscript>9</subscript> (Hyp) <subscript>3</subscript> }] and [Ir(COD)Cl] <subscript>2</subscript> , this methodology was expanded for the synthesis of eleven-vertex hetero-multimetallic clusters. A mechanism for the formation of these first examples of closo eleven-vertex Zintl clusters is proposed, informed by density functional theory calculations.<br /> (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)