Hydrogen-bonded cubanes and ladder fragments by analogy with the inorganic solid state.

By application of an analogy with the structures of alkali-metal phosphinimides, two hydrogen-bonded cubanes, [Ph(3)CNH(3)(+)X(-)](4) (X = Cl, Br), and one unprecedented four-rung ladder fragment, [Ph(3)CNH(3)(+)I(-)](4), have been prepared in the organic solid state.

Hydrogen-bonded cubanes in the crystal structure of 2,6-di(Pr(i))aniline hydrochloride and their inorganic analogues [M(2+)(2,6-di(Pr(i))C6H5N(2-))]4 (M = Sn, Pb).

The crystal structure of 2,6-di(Pr(i))aniline hydrochloride contains hydrogen-bonded cubanes analogous to those in the complexes [M(2+)(2,6-di(Pr(i))C6H5N(2-))]4, M = Sn, Pb.

Formation of double cubanes [Sn(7)(NR)(8)] in the reactions of pyridyl and pyrimidinyl amines with Sn(NMe(2))(2): a synthetic and theoretical study.

In contrast to the reactions of Sn(NMe(2))(2) with unfunctionalized primary amines (RNH(2)), which yield the simple imido Sn(II) cubanes [SnNR](4), the reactions of 2-pyridyl or 2-pyrimidinyl amines give the mixed-oxidation-state Sn(II)/Sn(IV) double cubanes [Sn(7)(NR)(8)]. In addition to [Sn(7)[2-N(5-Mepy)](8)] x 2thf (1 x 2thf) (py = pyridine) and [Sn(7)[2-N(pm)](8)] x 0.33thf (2 x 0.33thf) (pm = pyrimidine), which were communicated previously, the syntheses and structures of the new complexes [Sn(7)[2-N(4-Mepm)](8)] x 2thf (3 x 2thf), [Sn(7)[2-N(4,6-Me(2)pm)](8)] x 4thf (4 x 4thf), [Sn(7)[2-N(4-Me-6-MeO-pm)](8)] (5), and [Sn(7)[2-N(4-MeO-6-MeO-pm)](8)] (6) are reported. Model DFT calculations on the reactions of Sn(NMe(2))(2) with 2-pmNH(2) or PhNH(2), producing the cubanes [Sn[2-N(pm)]](4) and [SnNPh](4) (respectively), and the corresponding double cubanes [Sn(7)[2-N(pm)](8)] and [Sn(7)(NPh)(8)], show that the presence of intramolecular Sn...N bonding which spans the cubane halves of the complexes is crucial to the formation of the double-cubane structure.