Hayes, Paul

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Rhodium-mediated dehydrogenation of hydroboranes and group 14 compounds: base-stabilized silylene and germylene complexes vs. transmetalation
(Wiley, 2024) Hayes, Paul G.; Hsiang, Shou-Jen
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.