Synthesis and Reactivity of Multiple Phosphine‐Functionalized Nonagermanide Clusters

Herein we report on the synthesis of the first multiple phosphine‐substituted nonagermanide clusters in a one‐step reaction from K 4 Ge 9 . Their reactions towards various transition metal complexes show a large variety of reactive sites. The novel threefold phosphine‐functionalized [Ge 9 ] clusters [Ge 9 {PRR I } 3 ] − {R: N i Pr 2 ; R I : N i Pr 2 ( 1 a ) or t Bu ( 2 a )} are obtained by reaction of pristine [Ge 9 ] 4− clusters with the respective chlorophosphines. Subsequent reactions with NHC Dipp CuCl yield neutral compounds (NHC Dipp Cu)[Ge 9 {P(N i Pr 2 ) 2 } 3 ] ( 3 ) and (NHC Dipp Cu)[Ge 9 {P(N i Pr 2 ) t Bu} 3 ] ( 4 ), respectively. The reaction of neutral compound 3 with Cr(CO) 5 (thf) yields the first uncharged fivefold substituted [Ge 9 ] cluster (NHC Dipp Cu) 2 [Ge 9 {P(N i Pr 2 ) 2 } 2 Cr(CO) 5 ] ( 5 ) via a ligand exchange reaction at the [Ge 9 ] cluster core. Compounds 3 and 5 are characterized by single crystal structure determination.