Structures of indium trihalide complexes with phosphine oxides and dimethyl sulphoxide, with comments on the metal–oxygen bonding
- 1 January 1990
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 1,p. 219-227
- https://doi.org/10.1039/dt9900000219
Abstract
The crystal structures of several phosphine oxide and dimethyl sulphoxide complexes of indium trihalides have been determined. The compounds [InCl3(Me3PO)2(MeOH)], [InCl3-(Me3PO)2(H2O)]·H2O, [InCl3(PhMe2PO)3]·H2O, [InCl3(Me2SO)3], and [InBr3(Me2SO)3] are all fac octahedral, but [InCl3(Me3PO)3] has the mer configuration. Triphenylphosphine oxide yields ionic derivatives of the type [InX2(Ph3PO)4]+[InX4]–(X = Cl or Br). Methyldiphenylphosphine oxide gives covalent [InCl3(Ph2MePO)3], but ionic [InBr2(Ph2MePO)4]+[InBr4]–. The general development of six-co-ordination is possible through enlargement of the In–O–P bond angles, with individual values (range 135–160°) dependent upon steric interactions. The behaviour is consistent with a predominantly electrostatic metal–oxygen bonding. For the methanol and aqua complexes, determination of the positions of the hydroxylic protons established the ligand orientation with respect to the In–O vector. A quasi-ionic metal–ligand interaction is again in evidence.Keywords
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