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Homoleptic Phosphaalkyne Complexes of Silver(I)
Author(s) -
Rummel EvaMaria,
Mastrorilli Piero,
Todisco Stefano,
Latronico Mario,
Balázs Gábor,
Virovets Alexander V.,
Scheer Manfred
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201607725
Subject(s) - homoleptic , chemistry , yield (engineering) , molecule , stereochemistry , crystallography , medicinal chemistry , organic chemistry , metal , physics , thermodynamics
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.