Indium(III) halide-3,5-di-tert-butyl- o-benzosemiquinone systems
The reaction of InX 3 (X Cl, Br, I) with 2 mol of Na +TBSQ · − (TBSQ · − =3,5-di- t-butyl- o-benzosemiquinonate anion) yields solutions of the diradicals InX(TBSQ) 2, whose EPR spectra have been recorded. Addition of pyridine or γ-picoline (L) to such solutions produces adducts of the 3,5-di- t-b...
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Published in | Inorganica Chimica Acta Vol. 225; no. 1; pp. 207 - 213 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
Published |
Elsevier B.V
01.10.1994
|
Subjects | |
Online Access | Get full text |
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Summary: | The reaction of InX
3 (X Cl, Br, I) with 2 mol of Na
+TBSQ
·
− (TBSQ
·
− =3,5-di-
t-butyl-
o-benzosemiquinonate anion) yields solutions of the diradicals InX(TBSQ)
2, whose EPR spectra have been recorded. Addition of pyridine or γ-picoline (L) to such solutions produces adducts of the 3,5-di-
t-butylcatecholate-indium(III) halide, of the type In(TBC)XL
n
. The mechanism of these reactions, and of the related ligand replacement and disproportionation equilibria, is discussed in terms of internal one-electron transfer processes. The compound In(TBC)(pic)
2·DMF has been the subject of an X-ray crystallographic study. The substance forms monoclinic crystals, space group
P2
1/
n with
a=12.992(5),
b=13.923(4),
c=18.491(4) Å, β=98.82(2)
o,
Z=4,
R=0.053 for 3244 unique reflections. The molecule is dimeric, with a central In
2O
2 ring, involving six-coordinate indium(III). |
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ISSN: | 0020-1693 1873-3255 |
DOI: | 10.1016/0020-1693(94)04049-4 |