The Synthesis and Structure of Group 5 Metal Alkyl and Alkylidene Complexes containing 2,6-Dialkylphenoxide Ligands: X-Ray Crystal Structures of , , and t2-2,6)2(=CHSiMe3)(CH2SiMe3)>

DOI: 10.1039/DT9870000155

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 155 - 162 (1987)

Update date:2022-08-02

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Authors:

Chamberlain, Linda R.

Rothwell, Ian P.

Folting, Kristen

Huffmann, John C.

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Article abstract of DOI:10.1039/DT9870000155

A number of alkyl and alkylidene complexes of niobium and primarily tantalum containing 2,6-dialkylphenoxide ligation, OC6H3R2-2,6 (R = Me, Prⁱ, or Bu^t) have been synthesized and characterized.For the sterically less demanding 2,6-dimethyl- and 2,6-di-isopropyl-phenoxides a series of compounds (R' = H, SiMe3, or Ph) can be readily obtained by alkylation of the corresponding mixed chloro-aryloxide.The remaining two aryloxides are more resistant to further substitution.Spectroscopic evidence supports the ?-bonded compounds adopting a trigonal-bipyramidal structure with trans-axial aryloxide ligands.This structure was confirmed by a single-crystal X-ray diffaction study on .The di- and mono-alkyls and have also been isolated and the latter shown to adopt a square-pyramidal structure in the solid state with an axial methyl group.In contrast the reaction of t2-2,6)2Cl3> with Li(CH2SiMe3) or Mg(CH2Ph)2 leads to the mixed alkyl-alkylidene complexes t2-2,6)2(=CHR')(CH2R')> (R' = SiMe3 or Ph).The presence of the alkylidene functional group was confirmed both spectroscopically and by a single-crystal X-ray diffraction study on the trimethylsilyl derivative.A related complex, i2-2,6)2(=CHSiMe3)(CH2SiMe3)>, was obtained by photolysis of i2-2,6)2(CH2SiMe3)3>.

Full text of DOI:10.1039/DT9870000155

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