Stoichiometric reactivity of dialkylamine boranes with alkaline earth silylamides


Hill, M. S., Hodgson, M., Liptrot, D. J. and Mahon, M. F., 2011. Stoichiometric reactivity of dialkylamine boranes with alkaline earth silylamides. Dalton Transactions, 40 (30), pp. 7783-7790.

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Reactions of beta-diketiminato group 2 silylamides, [HC{(Me)CN(2,6-(i)Pr(2)C(6)H(3))}(2)M(THF)(n){N(SiMe(3))(2)}] (M = Mg, n = 0; M = Ca, Sr, n = 1), and an equimolar quantity of pyrrolidine borane, (CH(2))(4)NH center dot BH(3), were found to produce amidoborane derivatives of the form [HC{(Me)CN(2,6-(i)Pr(2)C(6)H(3))}(2)MN(CH(2))(4)center dot BH(3)]. In reactivity reminiscent of analogous reactions performed with dimethylamine borane, addition of a second equivalent of (CH(2))(4)NH center dot BH(3) to the Mg derivative induced the formation of a species, [HC{(Me) CN(2,6-(i)Pr(2)C(6)H(3))}(2)Mg{N(CH(2))(4)BH(2)NMe(2)BH(3)}], containing an anion in which two molecules of the amine borane substrate have been coupled together through the elimination of one molecule of H(2). Both this species and a calcium amidoborane derivative have been characterised by X-ray diffraction techniques and the coupled species is proposed as a key intermediate in catalytic amine borane dehydrocoupling, in reactivity dictated by the charge density of the group 2 centre involved. On the basis of further stoichiometric reactions of the homoleptic group 2 silylamides, [M{N(SiMe(3))(2)}(2)] (M= Mg, Ca, Sr, Ba), with (CH(3))(2)NH center dot BH(3) and (i)Pr(2)NH center dot BH(3) reactivity consistent with successive amidoborane beta-hydride elimination and [R(2)N=BH(2)] insertion is described as a means to induce the B-N dehydrocoupling between amine borane substrates.


Item Type Articles
CreatorsHill, M. S., Hodgson, M., Liptrot, D. J. and Mahon, M. F.
Related URLs
DepartmentsFaculty of Science > Chemistry
ID Code25260


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