Low‐Valent Group 14 NHC‐Stabilized Phosphinidenide ate Complexes and NHC‐Stabilized K/P‐Clusters

The N‐heterocyclic carbene (NHC)‐stabilized phosphinidenide, SIMesPK [SIMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolidine‐2‐ylidene], was used as an (NHC)P‐transfer reagent for the synthesis of the low‐valent Group 14 ate complexes K[(SIMesP) 3 E] (E=Ge: 2 , Sn: 3 , Pb: 4 ), which were characterized by 1 H NMR, 31 P NMR, IR spectroscopy as well as elemental and X‐ray analysis. Furthermore, SIMesPK was used in reactions with potassium amides and alkoxides to form the molecular phosphorus–potassium clusters [K 4 (SIMesP) 2 (hmds) 2 ] [ 5 , hmds=N(SiMe 3 ) 2 ] and [K 6 (SIMesP) 2 (O t Bu) 4 ] ( 6 ). Finally, the reaction of SIMesPK with Li[Al(OC 4 F 9 ) 4 ] led to the potassium‐rich ionic compound [(SIMesP) 4 K 5 ][Al(OC 4 F 9 ) 4 ] ( 7 ).