Preparation and structural organisation of heteroleptic tetraphenylantimony(V) complexes comprising unidentately and bidentately coordinated O, O′-dialkyldithiophosphate groups: Multinuclear ( 13C, 31P) CP/MAS NMR and single-crystal X-ray diffraction studies
Crystalline heteroleptic dialkyldithiophosphate tetraphenylantimony(V) complexes of the general formula [Sb(C 6H 5) 4{S 2P(OR) 2}] (R = C 3H 7, i-C 4H 9) have been prepared and studied by 13C and 31P CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. Unexpected structural distinctions wer...
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Veröffentlicht in: | Inorganica Chimica Acta 2007-06, Vol.360 (9), p.2897-2904 |
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Zusammenfassung: | Crystalline heteroleptic dialkyldithiophosphate tetraphenylantimony(V) complexes of the general formula [Sb(C
6H
5)
4{S
2P(OR)
2}] (R
=
C
3H
7,
i-C
4H
9) have been prepared and studied by
13C and
31P CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. Unexpected structural distinctions were discovered on these chemically related compounds, which are defined by the principally different coordination modes of
O,
O′-dipropyldithiophosphate and
O,
O′-di-
iso-butyldithiophosphate ligands in their molecular structures (i.e.,
S,
S′-bidentate chelating and
S-unidentately coordinated, respectively).
31P Chemical shift anisotropy parameters (
δ
aniso and
η) calculated from spinning sideband manifolds in MAS NMR spectra are remarkably different for phosphorus sites in both species of dithiophosphate ligands of these tetraphenylantimony(V) compounds.
O,
O′-dipropyldithiophosphate and
O,
O′-di-
iso-butyldithiophosphate (Dtph) tetraphenylantimony(V) complexes of the general formula [Sb(C
6H
5)
4{S
2P(OR)
2}] (R
=
C
3H
7,
i-C
4H
9) were prepared and studied by means of
13C,
31P CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. Distorted octahedral and trigonal bipyramidal molecular structures have been established for prepared complexes. These unexpected structural distinctions between chemically related compounds are defined by the principally different coordination modes of
O,
O′-dipropyldithiophosphate and
O,
O′-di-
iso-butyldithiophosphate ligands in their molecular structures (i.e.,
S,
S′-bidentate chelating and
S-unidentately coordinated, respectively). To characterise quantitatively phosphorus sites in both species of dithiophosphate ligands,
31P chemical shift anisotropy parameters (
δ
aniso and
η) were calculated from spinning sideband manifolds in MAS NMR spectra. The
31P chemical shift tensors for the bidentate chelating and unidentately coordinated dithiophosphate ligands display a profoundly rhombic and nearly axially symmetric characters, respectively. |
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ISSN: | 0020-1693 1873-3255 1873-3255 |
DOI: | 10.1016/j.ica.2007.02.044 |