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Issue 30, 2020

Exohedral functionalization vs. core expansion of siliconoids with Group 9 metals: catalytic activity in alkene isomerization

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Abstract

Taking advantage of pendant tetrylene side-arms, stable unsaturated Si6 silicon clusters (siliconoids) with the benzpolarene motif (the energetic counterpart of benzene in silicon chemistry) are successfully employed as ligands towards Group 9 metals. The pronounced σ-donating properties of the tetrylene moieties allow for sequential oxidative addition and reductive elimination events without complete dissociation of the ligand at any stage. In this manner, either covalently linked or core-expanded metallasiliconoids are obtained. [Rh(CO)2Cl]2 inserts into an endohedral Si–Si bond of the silylene-functionalized hexasilabenzpolarene leading to an unprecedented coordination sphere of the Rh centre with five silicon atoms in the initial product, which is subsequentially converted to a simpler derivative under reconstruction of the Si6 benzpolarene motif. In the case of [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) a similar Si–Si insertion leads to the contraction of the Si6 cluster core with concomitant transfer of a chlorine atom to a silicon vertex generating an exohedral chlorosilyl group. Metallasiliconoids are employed in the isomerization of terminal alkenes to 2-alkenes as a catalytic benchmark reaction, which proceeds with competitive selectivities and reaction rates in the case of iridium complexes.

Graphical abstract: Exohedral functionalization vs. core expansion of siliconoids with Group 9 metals: catalytic activity in alkene isomerization

Supplementary files

Article information


Submitted
20 May 2020
Accepted
02 Jul 2020
First published
02 Jul 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 7782-7788
Article type
Edge Article

Exohedral functionalization vs. core expansion of siliconoids with Group 9 metals: catalytic activity in alkene isomerization

N. E. Poitiers, L. Giarrana, V. Huch, M. Zimmer and D. Scheschkewitz, Chem. Sci., 2020, 11, 7782 DOI: 10.1039/D0SC02861D

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