The reaction of PCl3 with SnCl2 in THF solution, followed by treatment with dpp-BIAN (dpp = 2,6-i-Pr2C6H3), affords the phosphenium complex [(dpp-BIAN)P][SnCl5.THF]. The 31P chemical shift (delta 232.5) and the metrical parameters from a single-crystal X-ray diffraction study indicate that the oxidation state of phosphorus in this compound is +3. A similar conclusion was reached regarding the phosphorus oxidation state in [(dpp-BIAN)P][I3], which was prepared via the reaction of dpp-BIAN with PI3 in CH2Cl2 solution. The arsenium salt [(dpp-BIAN)As][SnCl5.THF] was prepared by treatment of AsCl3 with SnCl2 in THF solution, followed by the addition of dpp-BIAN. The X-ray crystal structure of this salt was determined, and the pattern of bond distances and angles indicates that arsenic is present in the +3 oxidation state.

Reduction of AsCl3 with SnCl2, followed by treatment of the "AsCl" with a 1,4-diimine results in electron transfer and formation of an arsenic(III) salt, while treatment of this arsenic(I) reagent or AsI3 with an alpha,alpha'-diiminopyridine ligand forms an arsenic(I) salt.

The reaction of TeI4 with the 2,6-diisopropylphenyl-substituted 1,2-bis(arylimino)acenaphthene ligand dpp-BIAN results in two-electron reduction of tellurium and formation of the complex (dpp-BIAN)TeI2, while treatment of TeCl4 with the alpha,alpha'-diiminopyridine ligand dpp-DIMPY causes C-H activation of an imino methyl group.

The new Ar-BIAN complexes [(mes-BIAN)InCl(3)(THF)] (1), [(mes-BIAN)(2)Tl][PF(6)] (2), [(dipp-BIAN)SnCl(4)] (3), [(dipp-BIAN)SbCl(3)] (4), [(dipp-BIAN)BiCl(3)] (5) and [(mes-BIAN)BiCl(3)] (6) have been prepared by treatment of the neutral mes- and dipp-substituted BIAN ligands with the p-block reagents InCl(3), TlPF(6), SnCl(4), SbCl(3), and BiCl(3). The molecular structures of complexes 1-6 have been determined by single-crystal X-ray diffraction methods. However, only the atom connectivity was established for 5.

The synthesis of the organotin-substituted crown ethers PhThe compounds are characterized by elemental analyses and 1 H, 13 C, 19 F, 23 Na, and 119 Sn NMR spectroscopy and in the case of compound 4 also by 119 Sn MAS NMR spectroscopy. Single-crystal X-ray diffraction analyses reveal for compounds 2-5 trigonal-bipyramidally configurated tin atoms with intramolecular Sn-O distances ranging between 2.530(2) (5) and 2.571(1) Å ( 4), whereas the tin atom in compound 1 shows a distorted tetrahedral configuration. The tin atoms in compounds 7 and 8 are hexacoordinated with intramolecular Sn-O distances ranging between 2.473(1) (7) and 2.522(1) Å ( 7). NMR spectroscopy reveals the ability of compound 4 to form, in competition with intramolecular O f Sn coordination, a ditopic complex with NaSCN.