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

Abstract

Treatment of P4 with 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 shorter than the shared electron-pair P-Au bond. The bonding in (XL)2InP(SnPh3)2 was also interrogated using (31)P and (13)C 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.

Isolation of Au-, Co-η1PCO and Cu-η2PCO complexes, conversion of an Ir–η1PCO complex into a dimetalladiphosphene, and an interaction-free PCO anion

“…5 ). The trinuclear nature of 10 [(L b Au) 3 P], as determined by an X-ray diffraction study, is reminiscent of the rearrangement product of Ph 3 Sn(PCO), namely (Ph 3 Sn) 3 P. 2d , 17 Three gold atoms surround a single P atom, leading to a phosphine supported solely by metals. The 31 P NMR spectrum displays a signal at δ = –200 ppm, which is considerably high-field shifted compared to alkyl and aryl phosphines.…”

Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide

“…We began our investigation of P red activation by surveying approaches that were previously used for the activation of P white to form polyphosphides by using alkali metals, LiPH 2 , or sodium naphthalenide . By reacting P red with potassium metal in refluxing THF/DME (1:1 v/v; DME=1,2‐dimethoxyethane), we were able to obtain orange/red solutions that contained a mixture of soluble polyphosphide anions, specifically P 5 − , P 16 2− , and P 21 3− , according to the 31 P NMR spectra (Figure a).…”

Phosphanyl Cyanophosphide Salts: Versatile PCN Building Blocks

“…Zuschriften upon removal of the solvent. (Ph 3 Sn) 3 P [25] was identified as one of the decomposition products.…”