Solid-state and dynamic solution equilibria of bis(dibenzylamido) magnesium complexes: aggregation dependence on stoichiometry and denticity of donor solvent

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Clegg, W. and Craig, F.J. and Henderson, K.W. and Kennedy, A.R. and Mulvey, R.E. and O'Neil, P.A. and Reed, D. (1997) Solid-state and dynamic solution equilibria of bis(dibenzylamido) magnesium complexes: aggregation dependence on stoichiometry and denticity of donor solvent. Inorganic Chemistry, 36 (27). pp. 6238-6246. ISSN 1520-510X (http://dx.doi.org/10.1021/ic970912a)

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Abstract

Reaction of commercial Bu2Mg with 2 molar equiv of dibenzylamine gives the bis(amido)magnesium complex [{{(PhCH2)2N}2Mg}2], 1. Compound 1 is dimeric with three-coordinate magnesium in the crystalline state. Addition of 2 molar equiv of the monodentate donor solvents THF and HMPA to solutions of 1 affords the complexes [{{(PhCH2)2N}2MgâTHF}2], 2, and [{{(PhCH2)2N}2MgâHMPA}2], 4 respectively, which maintain the dimeric framework but increase the metal's coordination number to 4. Addition of 4 molar equiv of HMPA, or a 20-fold excess, of THF to 1 causes deaggregation of the dimer to the monomeric bis-solvates [{(PhCH2)2N}2- Mgâ2THF], 3, and [{(PhCH2)2N}2Mgâ2HMPA], 5. The chelating ligand TMEDA gives the monomer [{(PhCH2)2N}2MgâTMEDA], 6, on mixing with 1. 1H and 13C NMR spectroscopic studies reveal that dimer 1 is partially retained in arene solution but is in equilibrium with the unsolvated monomer [{(PhCH2)2N}2Mg], 7. Concentration studies on solutions of monosolvated dimer 4 show it to be in equilibrium with both the bissolvated monomer 5 and the unsolvated monomer 7. X-ray crystallographic determinations have been carried out on complexes 1, 2, and 4-6, and a comparative analysis of their structures is detailed. The bis(dibenzylamido)- magnesium system has shown remarkable structural flexibility with di-, tri-, and tetracoordination at the metal.

ORCID iDs

Clegg, W., Craig, F.J., Henderson, K.W., Kennedy, A.R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Mulvey, R.E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564, O'Neil, P.A. and Reed, D.;
  • Item type:Article
    ID code:1306
    Dates:
    Date
    Event
    1997
    Published
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user:Users 45 not found.
    Date deposited:26 Jun 2006
    Last modified:11 Nov 2024 08:12
    URI:https://strathprints.strath.ac.uk/id/eprint/1306
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