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.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.