A rearrangement of azobenzene upon interaction with an aluminum(I) monomer LAl {L = HC[(CMe)(NAr)(2]), Ar=2,6-iPr(2)C(6)H(3)

作者：Zhu HP; Chai JF; Fan HJ; Roesky HW^*; Nehete UN; Schmidt HG; Noltemeyer M

来源：European Journal of Inorganic Chemistry, 2005, (11): 2147-2150.

DOI：10.1002/ejic.200400922

• aluminum
• azobenzene
• N ligands
• rearrangement

Reaction of LA1 (1) or [LA1{eta';-C-2(SiMe3)(2)}] (2) (L = HC[(CMe)-(NAr)](2), Ar = 2,6-iPr(2)C(6)H(3)) with azobenzene affords a five-membered ring compound [LA1{N(H)-o-C6H4N(Ph))}] (3). In the formation of 3 a three-membered intermediate [LA1(eta(2)-N2Ph2)] (A) is suggested by a [1 + 2] cycloaddition reaction; A is not stable and further rearranges to 3. DFT calculations on similar compounds with modified L'; (L'; = HCl(CMe) (NPh)](2)] show that the complexation energy of the reaction of L';Al with azobenzene to form [L';A1(eta(2)-N2Ph2)] is about -39 kcal mol(-1), and the best estimate of the energy difference between [L';A1(eta(2)-N2Ph2)] and [L';A1{N(H)-o-C6H4N(Ph))] is -76 kcal mol(-1).

• 出版日期2005-6-6