title: 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.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139-4307, United States.
authors.forename: Christopher C
authors.initials: CC
authors.lastname: Cummins
authors.forename: Chao
authors.initials: C
authors.lastname: Huang
authors.forename: Tabitha J
authors.initials: TJ
authors.lastname: Miller
authors.forename: Markus W
authors.initials: MW
authors.lastname: Reintinger
authors.forename: Julia M
authors.initials: JM
authors.lastname: Stauber
authors.forename: Isabelle
authors.initials: I
authors.lastname: Tannou
authors.forename: Daniel
authors.initials: D
authors.lastname: Tofan
authors.forename: Abouzar
authors.initials: A
authors.lastname: Toubaei
authors.forename: Alexandra
authors.initials: A
authors.lastname: Velian
authors.forename: Gang
authors.initials: G
authors.lastname: Wu