Synthesis and reactivity of o-benzylphosphino- and o-α-methylbenzyl(N,N-dimethyl)amine-boranes.
The series of o-benzylphosphino-boranes, o-(R(2)B)C(6)H(4)CH(2)PtBu(2) (R = Cl 3, Ph 4, Cy 6, C(6)F(5) 7, Mes 8) and o-(BBN)C(6)H(4)CH(2)PtBu(2) (5), were synthesized from reactions of the respective chloroboranes with the lithiated benzyl-phosphine. In an analogous fashion, the α-methylbenzyl(N,N-dimethyl)amine-boranes o-(R(2)B)C(6)H(4)CH(Me)NMe(2) (R = Cl 10, Ph 11, Cy 12, C(6)F(5) 13, Mes 14) were prepared. While these species were inactive in the catalytic hydrogenation of tBuN═CHPh, compounds 7, 8, and 14 did react with H(2) at elevated temperatures (100 °C), resulting in the elimination of HC(6)F(5) and mesitylene, respectively. In the latter case, the species o-((Mes)HB)C(6)H(4)CH(Me)NMe(2) 15 was isolated. 14 was also shown to react with H(2)O to give the species o-((Mes)(HO)B)C(6)H(4)CH(Me)NMe(2) 16 with the loss of mesitylene. The structure of these compounds and the nature of these reactions were also probed spectroscopically, crystallographically, and computationally. The energies for the products of hydrogenation, the phosphonium and ammonium hydridoborates, were computed. In all cases, these products were endothermic with respect to the precursor phosphine-boranes and amine-boranes and H(2). The barriers to H(2) activation were found to be in the range of 24-38 kcal/mol. These theoretical studies also demonstrate that the steric bulk around the boron center dramatically affects the activation barrier for H(2) activation, while the Lewis acidity of the borane has the largest effect on the stabilization of the resulting onium-borohydride. In the case of the elimination reactions, the driving forces appear to be the loss of arene byproduct and formation of a strong donor-acceptor bond.
Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario M5S 3H6, Canada.
Zachariah M
ZM
Heiden
Michael
M
Schedler
Douglas W
DW
Stephan
D001555:Benzene Derivatives / Q000737:chemistry; D001593:Benzyl Compounds / Q000737:chemistry*; D001880:Boranes / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D004123:Dimethylamines / Q000737:chemistry*; D006358:Hot Temperature; D006865:Hydrogenation; D008956:Models, Chemical; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry*
D001555:Benzene Derivatives; D001593:Benzyl Compounds; D001880:Boranes; D004123:Dimethylamines; D009942:Organometallic Compounds; D010720:Phosphines; C010219:mesitylene; C034516:dimethylamine; C044646:phosphine