By harnessing the high energy of ball milling, the mechanochemical synthesis of s-block metal allyl complexes can be studied in the absence of coordinating solvents. Traditional solvent-based methods require the use of ethereal solvents due to reagent solubility constraints. The introduction of such solvents often results in the irreversible coordination to metal centers, which may influence both compound formation and reactivity. Through mechanochemical milling methods, ethereal solvents can be avoided entirely. In an attempt to isolate ether-free s-block complexes of bulky allyl complexes, reactions of metal halides with the potassium salt of the [1.3-(SiMe3)2C3H5]– anion (A′) were investigated. In place of the expected coordinately unsaturated [A′xM]n complexes, complexes that did not reflect the stoichiometric ratios of the starting reagents were obtained. The complexes obtained were found to be highly dependent upon the metal center and display structures unusual for organometallic s-block compounds. The synthesis, characterization and reactivity of these complexes will be discussed in order to demonstrate “new rules” that dictate mechanochemical organometallic synthesis and possible consequences from the removal of coordinating solvent.

S-block grind: Mechanochemical synthesis of bulky allyl complexes of the s-block metals

251st National Meeting (2016)

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