title: "Spontaneous" ambient temperature dehydrocoupling of aromatic amine-boranes.
abstract: The dehydrocoupling/dehydrogenation behavior of primary arylamine-borane adducts ArNH(2)⋅BH(3) (3 a-c; Ar = a: Ph, b: p-MeOC(6)H(4), c: p-CF(3)C(6)H(4)) has been studied in detail both in solution at ambient temperature as well as in the solid state at ambient or elevated temperatures. The presence of a metal catalyst was found to be unnecessary for the release of H(2). From reactions of 3 a,b in concentrated solutions in THF at 22 °C over 24 h cyclotriborazanes (ArNH-BH(2))(3) (7 a,b) were isolated as THF adducts, 7 a,b⋅THF, or solvent-free 7 a, which could not be obtained via heating of 3 a-c in the melt. The μ-(anilino)diborane [H(2)B(μ-PhNH)(μ-H)BH(2)] (4 a) was observed in the reaction of 3 a with BH(3)⋅THF and was characterized in situ. The reaction of 3 a with PhNH(2) (2 a) was found to provide a new, convenient method for the preparation of dianilinoborane (PhNH)(2)BH (5 a), which has potential generality. This observation, together with further studies of reactions of 4 a, 5 a, and 7 a,b, provided insight into the mechanism of the catalyst-free ambient temperature dehydrocoupling of 3 a-c in solution. For example, the reaction of 4 a with 5 a yields 6 a and 7 a. It was found that borazines (ArN-BH)(3) (6 a-c) are not simply formed via dehydrogenation of cyclotriborazanes 7 a-c in solution. The transformation of 7 a to 6 a is slowly induced by 5 a and proceeds via regeneration of 3 a. The adducts 3 a-c also underwent rapid dehydrocoupling in the solid state at elevated temperatures and even very slowly at ambient temperature. From aniline-borane derivative 3 c, the linear iminoborane oligomer (p-CF(3)C(6)H(4))N[BH-NH(p-CF(3)C(6)H(4))](2) (11) was obtained. The single-crystal X-ray structures of 3 a-c, 5 a, 7 a, 7 b⋅THF, and 11 are discussed.
authors.affiliation: School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.
authors.forename: Holger
authors.initials: H
authors.lastname: Helten
authors.forename: Alasdair P M
authors.initials: AP
authors.lastname: Robertson
authors.forename: Anne
authors.initials: A
authors.lastname: Staubitz
authors.forename: James R
authors.initials: JR
authors.lastname: Vance
authors.forename: Mairi F
authors.initials: MF
authors.lastname: Haddow
authors.forename: Ian
authors.initials: I
authors.lastname: Manners