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N-heterocyclic-carbene-induced monomerization of sterically encumbered dialkylmagnesium and dialkylmanganese polymers

Kennedy, Alan and Klett, Jan and Robertson, Stuart and Mulvey, Robert (2011) N-heterocyclic-carbene-induced monomerization of sterically encumbered dialkylmagnesium and dialkylmanganese polymers. European Journal of Inorganic Chemistry (30). pp. 4675-4679. ISSN 1434-1948

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The sterically encumbered polymeric dialkyl complexes [M(CH2SiMe3)(2)](infinity) [M = Mg, Mn-II] were deaggregated by the potent two-electron sigma-donor, 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene (IPr), to yield the first examples of the monomeric three-coordinate [M(CH2SiMe3)(2)]center dot donor complexes [M = Mg (1); Mn (2)]. Similarly, monomeric three-coordinate species M[CH(SiMe3)(2)](2)center dot IPr [M = Mg, (3); Mn, (4)] were obtained from the bulkier disilyl-substituted alkyl [CH-(SiMe3)(2)] congeners M[CH(SiMe3)(2)](2)center dot ether by displacement of the ether by IPr. Complexes 1-4, which represent rare examples of N-heterocyclic-carbene-stabilized dialkylmagnesium and dialkylmanganese species, were crystallographically characterized; the diamagnetic magnesium complexes were also characterized in an arene solution by H-1 and C-13 NMR spectroscopy.