Rhodium-mediated dehydrogenation of hydroboranes and group 14 compounds: base-stabilized silylene and germylene complexes vs. transmetalation
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Date
2024
Authors
Hayes, Paul G.
Hsiang, Shou-Jen
Journal Title
Journal ISSN
Volume Title
Publisher
Wiley
Abstract
Monocarbonyl rhodium complex LRh(CO), 1, which is stabilized
by a pyrrole-based bis(phosphinimine) pincer ligand (L=k3-
NNN’=2,5-[iPr2P=N(4-iPrC6H4)]2-N’(C4H2) ), serves as a versatile
platform for the dehydrogenation of group 14 substrates.
Reaction with primary and secondary silanes and germanes
(MesSiH3, Et2SiH2, Ph2GeH2, tBuGeH3; Mes=mesityl) liberates H2
and yields base-stabilized tetrylene compounds of the form k2-
L(CO)Rh(ER2) (E=Si: R=Mes, H, 2; R=Et, 5; E=Ge: R=Ph, 6; R=
tBu, H, 8). The “:ER2” fragment in these species bridges between
the rhodium center and a phosphinimine donor. Preliminary
reactions between pinacol (Pin) and k2-L(CO)Rh(ER2), E=Si, Ge,
indicate that such complexes can serve as silylene and
germylene synthons, releasing :ER2 and catalytically generating
PinER2. In contrast, combination of complex 1 and MesGeH3
does not yield the anticipated dehydrogenation product, but
rather, transmetalation similar to that observed upon reaction
between 1 and 3,5-dimethylphenylborane prevails.
Description
Open access article. Creative Commons Attribution Non-Commercial NoDerivs License applies
Keywords
Dehydrogenation , Germylene , Rhodium , Silylene , Transmetalation
Citation
Hsiang, S.-J., & Hayes, P. G. (2024). Rhodium-mediated dehydrogenation of hydroboranes and group 14 compounds: base-stabilized silylene and germylene complexes vs. transmetalation. Chemistry: A European Journal, 30(5), Article E20230430. https://doi.org/10.1002/chem.202304302