Background Co-Catalyzed Reaction

SCHEME 4. Molecular structures of BINAPO complexes. [X. Zhang, K. Mashima, K. Koyano, N. Sayo, H. Kumobayashi, S. Akutagawa, and H. Takaya, Tetrahedron Lett., 32, 7283 (1991). Reproduced by permission of Peigamon Press.] 

SCHEME 6. Asymmetric 1,3-hydrogen shift catalyzed by BINAP-Rh(I) complexes. 

Kinetics. Kinetic measurements using [Rh((S)-binap)(CH30H)2]C104 and geranylamine substrate indicate that (1) The initial phase of the reaction obeys the first-order rate law, but as the initial substrate concentration, [substrate]0, is increased, the rate starts to deviate from the first-order plots at a relatively early stage of the reaction, implying a product inhibition. (2) The dependence of the initial rate Rq on the initial 

31P NMR Study and the Catalytic Cycle. The square-planar d8 Rh+ complexes of the type [Rh(binap)S2]+ undergo ligand exchange reac- 

3iP-NMR spectra of a 1 5 mixture of the BINAP-Rh+ complex and triethylamine in acetone-d6  

---