Insertion reactions ketones into metal-ligand bonds

In transfer hydrogenation with 2-propanol, the chloride ion in a Wilkinson-type catalyst (18) is rapidly replaced by an alkoxide (Scheme 20.9). / -Elimination then yields the reactive 16-electron metal monohydride species (20). The ketone substrate (10) substitutes one of the ligands and coordinates to the catalytic center to give complex 21 upon which an insertion into the metal hydride bond takes place. The formed metal alkoxide (22) can undergo a ligand exchange with the hydride donor present in the reaction mixture, liberating the product (15). 

The electrophile ftat modifies a coordinated ligand can be a proton, a strong Lewis acid, or an unsaturated electrophile. Examples of Lewis acids include tiityl cahon or per-fluoroarylboranes, and examples of unsaturated electrophiles include CO, SO, isocyanates, aldehydes, ketones, and related compoimds. Reactions of these electrophiles can lead to the formation of catioruc metal complexes by abstraction of a hydride or hydrocarbyl group by the Lewis acid, or they can lead to products from insertion of the unsaturated electrophile into the metal-carbon bond. These reactions are sho-wn generically in Equations 12.1-12.3. 

The reactivity of the cationic Zr complexes is a direct consequence of their Lewis acidity see Lewis Acids Bases) (i) various substitution reactions can occur into the Zr-solvent weak bond, (ii) unsatnrated substrates (CO, alkenes, alkynes, or ketones) insert into the Zr-C bond, potentially leading to polymerization reactions (see Section 8.2), (iii) new organic ligands obtained after reaction in the coordination sphere of the metal can be spontaneously released by /3-H elimination see -Hydride Elimination), or (iv) C-H bond activation of suitable ligands can occur. 

C3-symmetrical tripodal ligands have been used to obtain amido complexes of family (86). If chiral substituents are present in the ligand periphery, some stereo discrimination is observed in the reaction with several chiral ketones and aldehydes. On the other hand, such systems can generate early-late heterobimetallics with metal-metal bonds (equation 41). Reaction of (91) with MeNC as well as the heteroallenes CO2, CS2, RNCO and RNCS led to insertion into the polar metal-metal bond. Tris (pyrazolyl) borate see Tris(pyrazolyI)borates) Zr and Hf complexes are other interesting examples of the type (86). In combination with MAO, they give promising results in ethylene and ethylene/hexene polymerizations. Substitution of these sterically crowded ligands allows adjustements of the environment of the active site to the... 

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