The Stannylphosphide Anion Reagent Sodium Bis(triphenylstannyl) Phosphide: Synthesis, Structural Characterization, and Reactions with Indium, Tin, and Gold Electrophiles

National Science Foundation [CHE-1111357]; China Scholarship Council; NSERC of CanadaTreatment of P-4 with in situ generated [Na][SnPh3] leads to the formation of the sodium monophosphide [Na][P(SnPh3)(2)] and the Zintl salt [Na](3)[P-7]. The former was isolated in 46% yield as the crystalline salt [Na(benzo-15-crown-5)][P(SnPh3)(2)] and used to prepare the homoleptic phosphine P(SnPh3)(3), isolated in 67% yield, as well as the indium derivative (XL)(2)InP(SnPh3)(2) (XL = S(CH2)(2)NMe2), isolated in 84% yield, and the gold complex (Ph3P)AuP(SnPh3)(2). The compounds [Na(benzo-15-crown-5)][P(SnPh3)(2)], P(SnPh3)(3), (XL)(2)InP(SnPh3)(2), and (Ph3P)AuP(SnPh3)(2) were characterized using multinuclear NMR spectroscopy and X-ray crystallography. The bonding in (Ph3P)AuP(SnPh3)(2) was dissected using natural bond orbital (NBO) methods, in response to the observation from the X-ray crystal structure that the dative P -> Au bond is slightly shorter than the shared electron-pair P-Au bond. The bonding in (XL)(2)InP(SnPh3)(2) was also interrogated using P-31 and C-13 solid-state NMR and computational methods. Co-product [Na](3)[P-7] was isolated in 57% yield as the stannyl heptaphosphide P-7(SnPh3)(3), following salt metathesis with ClSnPh3. Additionally, we report that treatment of P-4 with sodium naphthalenide in dimethoxyethane at 22 degrees C is a convenient and selective method for the independent synthesis of Zintl ion [Na](3)[P-7]. The latter was isolated as the silylated heptaphosphide P-7(SiMe3)(3), in 67% yield, or as the stannyl heptaphosphide P-7(SnPh3)(3) in 65% yield by salt metathesis with ClSiMe3 or ClSnPh3, respectively

The Stannylphosphide Anion Reagent Sodium Bis(triphenylstannyl) Phosphide: Synthesis, Structural Characterization, and Reactions with Indium, Tin, and Gold Electrophiles

Treatment of P₄with in situ generated [Na]­[SnPh₃] leads to the formation of the sodium monophosphide [Na]­[P­(SnPh₃)₂] and the Zintl salt [Na]₃[P₇]. The former was isolated in 46% yield as the crystalline salt [Na­(benzo-15-crown-5)]­[P­(SnPh₃)₂] and used to prepare the homoleptic phosphine P­(SnPh₃)₃, isolated in 67% yield, as well as the indium derivative (XL)₂InP­(SnPh₃)₂ (XL = S­(CH₂)₂NMe₂), isolated in 84% yield, and the gold complex (Ph₃P)­AuP­(SnPh₃)₂. The compounds [Na­(benzo-15-crown-5)]­[P­(SnPh₃)₂], P­(SnPh₃)₃, (XL)₂InP­(SnPh₃)₂, and (Ph₃P)­AuP­(SnPh₃)₂ were characterized using multinuclear NMR spectroscopy and X-ray crystallography. The bonding in (Ph₃P)­AuP­(SnPh₃)₂ was dissected using natural bond orbital (NBO) methods, in response to the observation from the X-ray crystal structure that the dative P:→Au bond is slightly <i>shorter</i> than the shared electron-pair P–Au bond. The bonding in (XL)₂InP­(SnPh₃)₂ was also interrogated using ³¹P and ¹³C solid-state NMR and computational methods. Co-product [Na]₃[P₇] was isolated in 57% yield as the stannyl heptaphosphide P₇(SnPh₃)₃, following salt metathesis with ClSnPh₃. Additionally, we report that treatment of P₄ with sodium naphthalenide in dimethoxyethane at 22 °C is a convenient and selective method for the independent synthesis of Zintl ion [Na]₃[P₇]. The latter was isolated as the silylated heptaphosphide P₇(SiMe₃)₃, in 67% yield, or as the stannyl heptaphosphide P₇(SnPh₃)₃ in 65% yield by salt metathesis with ClSiMe₃ or ClSnPh₃, respectively

Emerging disease modifying therapies for older adults with Alzheimer disease: perspectives from the EuGMS special interest group in dementia

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