Homoleptic Phosphaalkyne Complexes of Silver(I)

Abstract By employing silver salts with a weakly coordinating anion Ag[A] ([A]=[FAl{OC 12 F 15 } 3 ], [Al{OC(CF 3 ) 3 } 4 ]), two phosphaalkynes could be coordinated side‐on to a bare silver(I) center to form the unprecedented homoleptic complexes [Ag(η 2 ‐P≡CtBu) 2 ][FAl{OC 12 F 15 } 3 ] ( 1 ) and [Ag(η 2 ‐P≡CtBu) 2 ][Al{OC(CF 3 ) 3 } 4 ] ( 2 ). DFT calculations show that the perpendicular arrangement in 1 is the minimum energy structure of the coordination of the two phosphaalkynes to a silver atom, whereas for 2 a unique square‐planar coordination mode of the phosphaalkynes at Ag + was found. Reactions with donor molecules yield the trigonally planar coordinated silver salts [((CH 3 ) 2 CO)Ag(η 2 ‐P≡CtBu) 2 ][FAl{OC 12 F 15 } 3 ] ( 3 ) and [(C 7 H 8 ) 2 Ag(η 2 ‐P≡CtBu)][FAl{OC 12 F 15 } 3 ] ( 4 ). All of the compounds were comprehensively characterized in solution and in the solid state.