Substitution of Hyp (Hyp = Si(SiMe)) at metalloid [Ge(Hyp)] clusters using phosphine stabilized Au()Cl

We present two new intermetalloid cluster compounds [( n Bu 3 P)AuGe 9 (Hyp) 2 Au(P n Bu 3 )] 2 ( 1 ) and [Au(iPr 2 POC 6 H 4 OPiPr 2 )AuGe 9 (Hyp) 2 ] 2 ( 2 ) which are obtained from the reaction of KGe 9 (Hyp) 3 (Hyp = Si(SiMe 3 ) 3 ) with the respective Au( i ) phosphine precursors. The products are characterized via X-ray crystal structure analysis and the reaction course is analysed via NMR spectroscopy. We also show that in the resulting compound 1 the hypersilyl substituents can be reintroduced via the reaction with Hyp-Cl to obtain n Bu 3 PAuGe 9 (Hyp) 3 . The reaction of [Ge 9 (Hyp) 3 ] − with ( n Bu 3 P)AuCl leads in the presence of free n Bu 3 P to [( n Bu 3 P)AuGe 9 (Hyp) 2 Au(P n Bu 3 )] 2 (Hyp = Si(SiMe 3 ) 3 ), providing further insight into the reaction mechanism of this build-up reaction.