10 research outputs found
Some ring expansions and related reactions of the phosphole system
The chemistry of simple phosphole derivatives is
comprehensively reviewed to the early part of 1970.
Using 1,2,5-triphenylphosphole and some of its
derivatives as starting materials, several ring expansion
and related reactions of the phosphole system have been i
studied. Thus, pyrolysis and photolysis of 3,4,5-
triphenyl-4-phosphabicyclo [3.1.0] hex-2-ene-4-oxide and
certain pyrazolino derivatives of 1,2,5-triphenylphosphole
oxide lead to the formation of compounds of
formula (see document for formula). These
compounds are shown to be derivatives of the 4,4’-
diphosphabi (cyclohexa-1,5-dienyl) and 4,4'-diphosphabi-
(cyclohexa-2,5-dienylidene) systems respectively and
possible mechanisms for the formation of these compounds
are discussed. Furthermore, the first of these compounds
may be converted into the second in an unusual reaction
in which lithium aluminium hydride acts as an oxidizing
agent.
The alkaline hydrolysis of 1-iodomethyl-l,2,5-
triphenylphospholium iodide is discussed as a possible
route to unsymmetrically substituted phosphorins
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Thallium pi-cation complexation by calix[4]tubes: Tl-205 NMR and X-ray evidence
Thallium cation complexation by calix[4]tubes has been investigated by a combination of (TI)-T-205, H-1 NMR and ES MS demonstrating the solution formation of a dithallium complex in which the cations are held in the calix[4]arene cavities. In addition, the structure of the complex has been determined in the solid state revealing the cations to be held exclusively by pi-cation interactions. Furthermore, this crystal structure has been used as the basis for molecular dynamics simulations to confirm that binding of the smaller K+ cation in the calix[4]tube cryptand like array occurs via the axial route featuring a g-cation intermediate