Synthesis of a Molecule with Four Different Adjacent Pnictogens

Abstract

The synthesis of a molecule containing four adjacent different pnictogens was attempted by conversion of a Group 15 allyl analogue anion [Mes*NAsPMes*](-) (Mes*=2,4,6-tri-tert-butylphenyl) with antimony(III) chloride. A suitable precursor is Mes*N(H)AsPMes* (1) for which several syntheses were investigated. The anions afforded by deprotonation of Mes*N(H)AsPMes* were found to be labile and, therefore, salts could not be isolated. However, the in situ generated anions could be quenched with SbCl3 , yielding Mes*N(SbCl2 )AsPMes* (4).

Investigation on Arsenic−Antimony‐ and Arsenic−Bismuth Bond Containing Interpnictogen Chain Molecules

“…In the 1 H NMR spectra of 1 the signal of the tert-butyl groups located at the antimony atom split up in a pair of singlets with an integral of 9 each. The same was observed in the 13 C NMR spectrum for the signals of the methyl groups as well as for the quaternary carbon atoms located at Sb. Similar observations were also made with the lighter homologues tBu 2 EP(H)tBu (E = As, Sb).…”

Dichloro‐Cycloazatriphosphane: The Missing Link between N2P2 and P4 Ring Systems in the Systematic Development of NP Chemistry

“…This weakening of one P−Cl bond emphasizes the instability of compound 10Mes* with respect to the previously discussed isomerization reactions. Also, the electronic situation is in contrast to related compounds of heavier pnictogens such as TerNNN(ECl 2 )Ter (E=P, As, Sb, Bi), TerNPN(SbCl 2 )Ter or TerPAsN(SbCl 2 )Ter, where the coplanar σ *(P−Cl) orbital acted as a σ acceptor for the in‐plane LP at the opposite N or P atom …”

Synthesis of a Molecule with Five Different Adjacent Pnictogens

“…An apparent reason might by the intrinsic instability of covalent Bi−X bonds (X=any other main group element) arising from the metallic character of bismuth and its diffuse valence orbitals. To the best of our knowledge only two quaternary interpnictogen compounds are described in the literature up to now: SbCl 2 N(Mes*)AsPMes* (Mes*=2,4,6‐tri‐ tert ‐butyl‐phenyl) by A. Schulz and [ClAs( μ ‐N(=PMe 3 )) 2 SbCl 4 ][SbCl 6 ] by K. Dehnicke . Both compounds do not contain the heaviest pnictogene bismuth.…”