Solvent induced disproportionation of alkyl(amido)magnesium species containing a (2-pyridyl)amido unit : Synthetic, theoretical and NMR spectroscopic studies of bis(amido)magnesium compounds

Henderson, K.W. and Mulvey, Robert and Dorigo, A.E. (1996) Solvent induced disproportionation of alkyl(amido)magnesium species containing a (2-pyridyl)amido unit : Synthetic, theoretical and NMR spectroscopic studies of bis(amido)magnesium compounds. Journal of Organometallic Chemistry, 518 (1-2). pp. 139-146. ISSN 0022-328X (https://doi.org/10.1016/0022-328X(96)06202-X)

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Abstract

Reaction of R(2-pyr)NH (where R = Me, Ph or 2-pyr) with 'Bu(2)Mg' in an ether-free environment yields the corresponding alkyl(amido)magnesium derivative [{R(2-pyr)NMgBu}(n)]. When polar solvent is added to these species only bis(amido)magnesium compounds separate from solution and not the expected solvated alkyl(amido) derivatives. Isolation of one such alkyl(amido) compound prior to reaction with donor solvent proves that the mixed anion species do indeed exist, However, when polar molecules are introduced a disproportionation reaction ensues, yielding the homoleptic compounds [{R(2)Mg .(S)(x)}(n)] and [{(R(2)N)(2)Mg .(S)(x)}(n)], where S is THF, TMEDA or PMDETA. Theoretical calculations likewise show that the disproportionation reaction of model compounds closely related to our systems is strongly exothermic. A H-1/C-13 NMR spectroscopic study was used to assign the nature of the bis(amido) species in solution. From these analyses it was possible to propose that the solvated bis(amido) derivatives assume a common structural motif, that of a monomer (n = 1) with a pseudo-octahedral magnesium center.

ORCID iDs

Henderson, K.W., Mulvey, Robert ORCID logoORCID: https://orcid.org/0000-0002-1015-2564 and Dorigo, A.E.;
CORE (COnnecting REpositories)