Directed Synthesis of Phosphorus-Carbon Cage Compounds—A Challenge in Organophosphorus Chemistry [1]

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(η2‐P≡CtBu)2][FAl{OC12F15}3] (1) and [Ag(η2‐P≡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)2CO)Ag(η2‐P≡CtBu)2][FAl{OC12F15}3] (3) and [(C7H8)2Ag(η2‐P≡CtBu)][FAl{OC12F15}3] (4). All of the compounds were comprehensively characterized in solution and in the solid state.

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Homoleptic Phosphaalkyne Complexes of Silver(I)

Rummel

Mastrorilli

Todisco

et al. 2016

Angewandte Chemie

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Homoleptic Phosphaalkyne Complexes of Silver(I)

et al. 2016

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By employing silver salts with a weakly coordinating anion Ag[A] ([A]=[FAl{OC F } ], [Al{OC(CF ) } ]), two phosphaalkynes could be coordinated side-on to a bare silver(I) center to form the unprecedented homoleptic complexes [Ag(η -P≡CtBu) ][FAl{OC F } ] (1) and [Ag(η -P≡CtBu) ][Al{OC(CF ) } ] (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 ) CO)Ag(η -P≡CtBu) ][FAl{OC F } ] (3) and [(C H ) Ag(η -P≡CtBu)][FAl{OC F } ] (4). All of the compounds were comprehensively characterized in solution and in the solid state.

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A survey of the behavior of the hydroxybisphosphonic function in crystallized acids, metallic salts, and some related compounds

Silvestre

Dao

Leroux

2001

Heteroatom Chemistry

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Directed Synthesis of Phosphorus-Carbon Cage Compounds—A Challenge in Organophosphorus Chemistry [1]

Cited by 5 publications

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Homoleptic Phosphaalkyne Complexes of Silver(I)

Homoleptic Phosphaalkyne Complexes of Silver(I)

Homoleptic Phosphaalkyne Complexes of Silver(I)

A survey of the behavior of the hydroxybisphosphonic function in crystallized acids, metallic salts, and some related compounds

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