Addition of aluminium, zinc and magnesium hydrides to rhodium(iii)† †Electronic supplementary information (ESI) available. CCDC 1047853–1047855 1056989. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01309g Click here for additional data file. Click here for additional data file.

We report the addition of M–H bonds (M1⁄4 Al, Zn, Mg) to a Rh(III) intermediate generated from the reductive elimination of triethylsilane from [Cp*Rh(H)2(SiEt3)2]. A series of new heterobimetallic complexes possessing Rh–M bonds have been isolated and characterised by a number of spectroscopic (H, Si, C, Rh NMR, infrared, and X-ray diffraction) and computational techniques (NBO and QTAIM analysis). Experimental and computational data are consistent with cleavage of theM–Hbond upon addition to rhodiumwith formation of new Rh–M and Rh–H bonds. Upon photolysis the Al analogue of this series undergoes a further elimination reaction producing triethylsilane and a highly unusual Rh2Al2H4 containing cluster proposed to contain an Al(I) bridging ligand.