Evaluation of the 2,6-Diisopropylphenylimido Ligand as a Steric Force in d1 and d2 Monomeric Octahedral Complexes of Tungsten

DOI: 10.1039/DT9950001907

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1907 - 1914 (1995)

Update date:2022-08-03

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Authors:

Clark, George R.

Nielson, Alastair J.

Rickard, Clifton E. F.

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Article abstract of DOI:10.1039/DT9950001907

Reduction of <2> with 2 equivalents of Na-Hg amalgam in the presence of phosphines gave the d¹ complexes (L = PMe3, PMe2Ph or PMePh2).The crystal structure of 1 shows the 2,6-diisopropylphenylimido ligand exerts a greater trans influence than a phenylimido ligand but only slightly more steric pressure.Solutions of complex 1 react with air to give 2 for which the crystal structure shows the OPMe3 ligand lying trans to the imido ligand.Reduction of <2> with 4 equivalents of Na-Hg amalgam in the presence of phosphines gave the d² complexes (L = PMe3 or PMe2Ph).Complex 3 reacts with alkynes L' to give the complexes (L' = PhC2Ph, MeC2Me or PhC2H) for which 1H and 13C-<1H> NMR spectral data were obtained.The crystal structure of 6 shows cis-chloro ligands, trans-phosphines and mutually cis-imido and alkyne ligands.The C(6) isopropyl group rotates to minimise the isopropyl group and PhC2H interaction.The complex can be prepared but not .Reduction of by Na-Hg amalgam in the presence of olefins gave the complexes (L' = CH2CH2 or CH2CHMe).A more bulky organoimido ligand or a large phosphine is needed to exert steric pressure in all the complexes prepared.

Full text of DOI:10.1039/DT9950001907

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