Structural and metal-halogen exchange reactivity studies of sodium magnesiate biphenolate complexes

Yeardley, Callum and Kennedy, Alan R. and Gros, Philippe C. and Touchet, Sabrina and Fairley, Michael and McLellan, Ross and Martínez-Martínez, Antonio J. and O'Hara, Charles T. (2020) Structural and metal-halogen exchange reactivity studies of sodium magnesiate biphenolate complexes. Dalton Transactions, 49 (16). pp. 5257-5263. ISSN 1477-9226 (https://doi.org/10.1039/D0DT00904K)

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Abstract

Bimetallic sodium magnesiates have been employed in metal-halogen exchange for the first time. Utilising the racemic phenoxide ligand 5,5´,6,6´-tetramethyl-3,3´-di-tert-butyl-1,1´-biphenyl-2,2´-diol [(rac)-BIPHEN-H2], the dialkyl sodium magnesiates [(rac)-BIPHEN]Na2MgBu2(TMEDA)2 3 and [(rac)-BIPHEN]Na2MgBu2(PMDETA)2 4 have been synthesised. Both 3 and 4 can be easily prepared through co-complexation of di-n-butylmagnesium with the sodiated (rac)-BIPHEN precursor which can be prepared in situ in hydrocarbon solvent. Prior to the main investigation, synthesis of the sodiated precursor [BIPHEN]2Na4(THF)4 1 was explored in order to better understand the formation of sodium magnesiates utilising the dianionic (rac)-BIPHEN ligand as the parent ligand. In addition, a BIPHEN-rich sodium magnesiate [BIPHEN]2Na2Mg(THF)4 2 was prepared and characterised, and its formation was rationalised. Complex 1 and 4 have also been fully characterised in both solid and solution state. In terms of onward reactivity, 3 and 4 have been tested as potential exchange reagents with aryl and heteroaryl iodides to produce aryl and heteroaryl magnesium phenoxides utilising toluene as a non-polar hydrocarbon solvent. Complex 3 reacted smoothly to give a range of aryl and heteroaryl magnesium phenoxides, whilst 4’s reactivity is more sluggish.

ORCID iDs

Yeardley, Callum, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Gros, Philippe C., Touchet, Sabrina, Fairley, Michael ORCID logoORCID: https://orcid.org/0000-0002-6021-0339, McLellan, Ross ORCID logoORCID: https://orcid.org/0000-0001-9700-0258, Martínez-Martínez, Antonio J. and O'Hara, Charles T.;
  • Item type:Article
    ID code:71935
    Dates:
    Date
    Event
    28 April 2020
    Published
    3 April 2020
    Published Online
    27 March 2020
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:31 Mar 2020 10:23
    Last modified:27 Nov 2024 01:17
    URI:https://strathprints.strath.ac.uk/id/eprint/71935
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