Homoleptic Silver Complexes of the Cages P 4 Se 3 and As 4 S 3

By reacting P 4 Se 3 and As 4 S 3 with Ag[Al(OR F ) 4 ] {–R F = –C(CF 3 ) 3 or – hfip [= –C(H)(CF 3 ) 2 ]} in suitable solvents, Ag(P 4 Se 3 )[Al(O hfip ) 4 ] ( 1 ), Ag(P 4 Se 3 ) 2 [Al(OR F ) 4 ] ( 2 ), Ag(P 4 Se 3 ) 3 [Al(OR F ) 4 ] ( 3 ), Ag 2 (As 4 S 3 ) 3 [Al(OR F ) 4 ] 2 ( 4 ) and Ag(As 4 S 3 ) 2 [Al(OR F ) 4 ] ( 5 ) were synthesized and characterized by SC‐XRD, Mass spectrometry, Raman spectroscopy as well as solution NMR spectroscopy. When using stronger coordinating anions, only P 4 Se 3 forms an isolable complex yielding 1 featuring a [Ag 2 (P 4 Se 3 ) 2 ] 2+ core capped by anions acting as the first example of P 4 Se 3 coordinating through selenium atoms. Upon using the weakly coordinating anion [Al{OC(CF 3 ) 3 } 4 ] – , the dimeric complexes 2 and 4 are accessible in dichloromethane or ortho ‐difluorobenzene ( o ‐dfb), respectively. Complex 2 shows isolated [Ag 2 (P 4 Se 3 ) 4 (CH 2 Cl 2 ) 2 ] 2+ dications with a [Ag 2 (P 4 Se 3 ) 2 ] 2+ core similar to 1 . Complex 4 shows isolated [Ag 2 (As 4 S 3 ) 3 ] 2+ dications featuring a weak argentophilic contact. All of these complexes include solvent molecules or anions in the coordination sphere of the metal. When switching to the polar yet non‐coordinating solvent SO 2 , the coordination spheres are filled with additional ligands and compounds 3 and 5 form. Complex 3 shows condensed [Ag(P 4 Se 3 ) 3 ] + units yielding a one dimensional chain and represents the first homoleptic metal(P 4 Se 3 ) complex. Complex 5 shows a similar paddle wheel structure as in 4 with interconnecting As 4 S 3 ligands and is the first known example of a homoleptic metal(As 4 S 3 ) complex.