Reaction of (dippp)Pd(Ph)Cl (1) with norbornene or styrene yields (dippp)PdCl2 (8) and (dippp)Pd(η2-olefin). Kinetic follow-up reveals fast formation of (dippp)Pd(phenylnorbornyl)-Cl (10), followed by its slow decomposition, with kinsertion = 0.50 × 10-3 L mol-1 s-1 and kdecomposition = 0.90 × 10-4 s-1. Phenylnorbornane and (with styrene) stilbenes are also formed. Faster reaction is observed with (dppp)Pd(Ph)Br (2) and faster still with (dippe)Pd(Cl (4) to yield, in the latter case, the stable (dippe)Pd(phenylnorbornyl)Cl (18). The rates of these reactions are strongly solvent dependent (DMF ≫ dioxane), are strongly retarded by added Cl-, and are unaffected by added phosphine, indicating that halide dissociation, followed by olefin coordination and rate-determining olefin insertion, are involved. In contrast, reaction of trans-(PiPr2 nBu)2Pd(Ph)X (X = Cl, 5; X = Br, 6) with norbornene (or styrene) involves phosphine dissociation and leads to formation of (PiPr2 nBu)2Pd(H)X. In the case of norbornene, β-carbon elimination of the unobserved intermediate phenylnorbornyl complexes followed by β-H elimination yields 1-methylene-2-phenylcyclohexenes. Complexes of the ligand dippb are unique in that both η1 and η2 coordination modes are easily accessible. While reaction products are similar to those obtained with dippp and dippe complexes, dependence of the reaction rate on reaction variables is intermediate between those observed for complexes of chelating and monodentate phosphines. The implications of these findings on catalysis are outlined.
|Number of pages||15|
|Publication status||Published - 1994|
ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry