摘要:
Me(2)AlH and Bu(2)(i)AlH were reacted with a series of nine aminoarsines, Me(2)AsR (R = NMe(2), NPr(n)2, NPr(i)2, NBu(n)2, NBu(i)2, NC4H8, NC5H10, NC6H12, and N(C2H4)(2)NMe), in C6D6 at room temperature, and the reactions were monitored by H-1 and C-13 NMR spectroscopy. The relative rates for initial As-N bond cleavage and final product formation were dependent on the steric requirements of the alkyl groups attached to aluminum and nitrogen in the starting materials. Overall rates were slower with Bu(2)(i)AlH than with Me(2)AlH for a given aminoarsine. For most of the reactions, the predominant Al-containing products were the dimeric aminoalane compounds, [Me(2)AlR](2) and [Bu(2)(i)AlR](2). Although AI-N bond formation was the prefered mode of reaction, Al-As bond formation was also observed when the bulky Pr-i and Bu(i) aminoarsine derivatives were used. The [Bu(2)(i)A1R](2) compounds were synthesized independently by the reaction of Bu(2)(i)AlH and the respective amine or, in the case of [Bu(2)(i)AlBu(2)(i)](2), by the reaction of Bu(2)(i)AlCl and LiNBu(2)(i). X-ray crystal structures were determined for the compounds [Me(2)AlNC(6)H(12)](2), [Me(2)AlN(C2H4)(2)NMe](2), [BU(2)(i)AlNMe(2)](2), and [Bd(2)(i)AlN-(C2H4)(2)NMe](2). All of the compounds have planar Al2N2 rings with the exception of [Bu(2)(i)AlN(C2H4)2NMe](2), which displays a puckered Al2N2 ring.