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Structural Investigations of the Organoantimony(V) Halides Ph4SbX and Ph3SbX2 (X = Cl, Br or I) in the Solid State and in Solution

DOI: 10.1039/DT9950002895

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2895 - 2900 (1995)

Update date:2022-08-05

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Authors:

Baker, Lisa-JaneBaker, Lisa-Jane

Rickard, Clifton E. F.Rickard, Clifton E. F.

Taylor, Michael J.Taylor, Michael J.

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Article abstract of DOI:10.1039/DT9950002895

X-Ray crystallography revealed a distorted trigonal-bipyramidal structure for Ph4SbI, with Sb-Cax 2.141(3), Sb-Ceq 2.103(3)-2.117(3) Angstroem and a long Sb-I distance of 3.341(1) Angstroem in monoclinic crystals of P21/n symmetry.Consideration of the weak Sb-X bonds in Ph4SbX (X = Cl, Br or I) leads to reassignment of their Raman spectra; Ph4SbI ionises forming (1+) in acetonitrile, as shown by 13C and 121Sb NMR spectra.The halide Ph3SbI2 is reported in two phases, yellow, orthorombic (Fdd2) crystals isomorphous with Ph3SbBr2 and off-white, cubic (P4332) crystals.In each the molecule is trigonal-bipyramidal, with axial Sb-I bonds of 2.865(1) Angstroem in the former and 2.885(1) Angstroem in the latter, and small differences in their respective bond angles.The phenyl groups of the cubic form are in the regular propeller arrangement whereas one group of the orthorhombic form has a reversed orientation.The vibrational spectra of the two forms differ slightly.

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