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Chem. Soc. 1998, 120, 4033–4034. S. J. Patel, T. F. Jamison, Angew. Chem. Int. Ed. 2003, 42, 1364–1367. A. Pelter, K. Smith, H. C. Brown, Borane Reagents in Best Synthetic Methods, Academic Press, 1988. (a) Y. Sato, T. Takanashi, M. Hoshiba, M. Mori, J. Organomet. Chem. 2003, 688, 36–48; (b) Y. Sato, N. Saito, M. Mori, J Org. Chem. 2002, 67, 656–662; (c) Y. Sato, M. Takimoto, M. Mori, Miwako. Yuki Gosei Kagaku Kyokaishi, 2001, 59, 576– 588; (d) M. Takimoto, Y. Hiraga, Y. Sato, M. Mori, Tetrahedron Lett.

The other extreme is the PF3 complex, which shows n(CO) values as high as 2110 cmÀ1 . 33(a)). This back donation compensates for the weak donative NiaP s-bonding that stems from the weak basicity associated with PF3 . Ph3 P is inferior to R3 P as a donative ligand but is superior as a p-acid ligand, because Ph3 P has the s à (P-Csp 2 ) lying lower than the s à (P-Csp 3 ) of R3 P. 33. The dp-s à back donation interaction (a) and the cone angle (b). R PF3 2110 2100 P O ν CO 2090 2080 P(CH2CCl3)3 P(C6F5)3 3 O P O O P(OPh)3 P(CH2CH2Cl)3 P(OMe)3 P(OMe)Ph2 2070 P(OEt)Ph2 PMe2Ph PMe3 HF F 3 PPh3 P(p-Tol)3 P(o-Tol)3 P(CH2Ph)3 P(NMe2)3 P(i-Pr)3 PCy3 2050 100 110 120 130 140 3 PPh2C6F5 P P(Et)3 P(Bu)3 2060 t-Bu 3 P(CH2CH2CN)3 P(O-i-Pr)3 P(OEt)3 P O P O P(O-p-Tol)3 P(O-o-Tol) 3 PMe2CF3 150 160 Θ Fig.

32. 32(b)). 32. 32 and reductive elimination of the thus-formed NaNiaH intermediate provides the final product with regeneration of NiPCy3. 30). 32(b)), but this is not the case. 30 unit [54]. 32 have the same electronic configuration; they differ only in the ring size, and this difference bestows each of them with unique roles in the catalytic cycle. 30 (Eqs. 32). 31 is productive and undergoes insertion of ethylene. An interesting point here is that in organometallic chemistry the Curtin–Hammett principle applies to configurational isomers, because organometallic configurational isomers can change one to another with activation energies within a few Kcal molÀ1 , in the same way that conformational isomers do in organic molecules [55].

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