biostudies-literatureTownrow OPEShell Global Solutions InternationalEngineering and Physical Sciences Research Council7626-7633https://www.ebi.ac.uk/biostudies/studies/S-EPMC9242017biostudies-literatureUnknown13(25)Ligand exchange reactions of [Rh(COD){η⁴-Ge₉(Hyp)₃}] with L-type nucleophiles such as PMe₃, PPh₃, IMe₄ (IMe₄ = 1,3,4,5-tetramethylimidazol-2-ylidene) or [W(Cp)₂H₂] result in the displacement of the COD ligand to afford clusters with coordinatively unsaturated trigonal pyramidal rhodium(i) centers [Rh(L){η³-Ge₉(Hyp)₃}]. These species can be readily protonated allowing access to cationic rhodium-hydride complexes, <i>e.g.</i> [RhH(PPh₃){η³-Ge₉(Hyp)₃}]⁺. These clusters act as catalysts in H/D exchange between H₂ and D₂ and alkene isomerisation, thereby illustrating that metal-functionaliChemical scienceZintl cluster supported low coordinate Rh(i) centers for catalytic H/D exchange between H₂ and D₂.PMC9242017EP/M024210Duckett SBGoicoechea JMTownrow OPEWeller ASfalseZintl cluster supported low coordinate Rh(i) centers for catalytic H/D exchange between H₂ and D₂.Ligand exchange reactions of [Rh(COD){η⁴-Ge₉(Hyp)₃}] with L-type nucleophiles such as PMe₃, PPh₃, IMe₄ (IMe₄ = 1,3,4,5-tetramethylimidazol-2-ylidene) or [W(Cp)₂H₂] result in the displacement of the COD ligand to afford clusters with coordinatively unsaturated trigonal pyramidal rhodium(i) centers [Rh(L){η³-Ge₉(Hyp)₃}]. These species can be readily protonated allowing access to cationic rhodium-hydride complexes, <i>e.g.</i> [RhH(PPh₃){η³-Ge₉(Hyp)₃}]⁺. These clusters act as catalysts in H/D exchange between H₂ and D₂ and alkene isomerisation, thereby illustrating that metal-functionali2022-01-01T00:00:00Z2022 Jun2026-05-09T23:42:50.524Z2025-04-04T22:13:21.39ZS-EPMC92420173587281010.1039/d2sc02552c