Abstract
By employing silver salts with a weakly coordinating anion Ag[A] ([A]=[FAl{OC12F15}(3)], [Al{OC(CF3)(3)}(4)]), two phosphaalkynes could be coordinated side-on to a bare silver-(I) center to form the unprecedented homoleptic complexes [Ag(eta(2)-P equivalent to CtBu)(2)][FAl{OC12F15}(3)] (1) and [Ag(eta(2)-P equivalent to CtBu)(2)]-[Al{OC(CF3)(3)}(4)] (2). DFT calculations show that the ...
Abstract
By employing silver salts with a weakly coordinating anion Ag[A] ([A]=[FAl{OC12F15}(3)], [Al{OC(CF3)(3)}(4)]), two phosphaalkynes could be coordinated side-on to a bare silver-(I) center to form the unprecedented homoleptic complexes [Ag(eta(2)-P equivalent to CtBu)(2)][FAl{OC12F15}(3)] (1) and [Ag(eta(2)-P equivalent to CtBu)(2)]-[Al{OC(CF3)(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 [((CH3)(2)CO) Ag(eta(2)-P equivalent to CtBu)(2)][FAl{OC12F15}(3)] (3) and [(C7H8)(2)Ag(eta(2)-P equivalent to CtBu)][FAl{OC12F15}(3)] (4). All of the compounds were comprehensively characterized in solution and in the solid state.
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