Organometallic radicals transition-metal compounds

Hydrocyanation is the addition of HCN across carbon-carbon or carbon-heteroatom multiple bonds to form products containing a new C-C bond. The majority of examples from organometallic chemistry involve the addition of HCN across carbon-carbon multiple bonds, as shown in Equations 16.2 and 16.3. Lewis acids and peptides have been used to catalyze the enantioselective addition of HCN to aldehydes and imines to form cyanohydrins and precursors to amino acids.The addition of HCN to unactivated olefins requires a catalyst because HCN is not sufficiently acidic to add directly to an olefin, and the C-H bond is strong enough to make additions by radical pathways challenging. However, a large number of soluble transition metal compounds catalyze the addition of HCN to alkenes and alkynes. 

Thus, as in the case of alkenes in the preceding chapter, we start with the radical type of activation that is much older. Transition-metal compounds play a key role in radical activation, because they provide very strong oxidants that can oxidize hydrocarbons either by (reversible) electron transfer or H-atom transfer (more rarely by hydride transfer). Biological oxidation of hydrocarbons involves reactive metal-0X0 species in methane mono-oxygenases and many related synthetic models, and a number of simple metal-oxo complexes also work. The clear criterion of distinction between an organometallic C-H activation and a radical activation is the above selectivity in activated C-H bonds. 

The first organometallic compound of the transition metals to be characterized (1827) was Zeise s salt, K[(C2H4)PtCl3]-H20 (Fig. 18.1). It forms when K2[PtCl4] in aqueous ethanol is exposed to ethylene (ethene) a dimeric Pt—C2H4 complex with Cl bridges is also formed. In both species, the ethylene is bonded sideways to the platinum(II) center so that the two carbon atoms are equidistant from the metal. This is called the dihapto-or T]2 mode. A ligand such as an allyl radical with three adjacent carbons directly bonded to a metal atom would be trihapto- or t 3, and so on. 

Organometallic compounds of transition metals with alkyl-to-metal bonds for many years were regarded as highly unstable substances and prone to dissociate into radicals that would couple or disproportionate, as illustrated by the following sequence ... 

Fluxional and Nonrigid Behavior of Transition Metal Organometallic ir-Complexes, 16, 211 Free Radicals in Organometallic Chemistry, 14, 345 Functionally Substituted Cyclopentadienyl Metal Compounds, 21,1... 

IV Electron transfer reactions of free radicals and metal complexes, including reactions of R with M +, e.g., oxidation by Cu2+ or reduction by Cr2+ (considered to be outside our scope unless M>+ represents an organometallic compound), and reactions of RMgX with transition metal complexes m, 129... 

Numerous transient paramagnetic compounds are known and some of these are also shown in Table IV there is an overlap with Section V, and Table IV does not duplicate material which is more conveniently treated later. The distinction is arbitrary, but we shall defer consideration of transient transition metal-centered radicals, e.g., Pt(I), if their formation is primarily of interest in connection with an organometallic mechanistic study, e.g., the oxidative addition of an alkyl halide to a Pt(0) substrate. The designation of metal oxidation state in Table IV is somewhat formal in many cases it might be more appropriate to describe a complex as derived from a paramagnetic ligand, such as a nitroxide or ketyl. 

Mashima, K., Nakayama, Y. and Nakamura, A. Recent Trends in Polymerization of a-Olefins Catalyzed by Organometallic Complexes of Early Transition Metals. Vol. 133, pp. 1-52. Matsumoto, A. Free-Radical Crosslinking Polymerization and Copolymerization of Multivinyl Compounds. Vol. 123, pp. 41-80. 

This principle links the typical organometallic oxidation state-based view of transition metal catalysis reactions best with the radical reaction manifold. At the end a table that links the typical radical reaction types to the different metals catalyzing them is provided. Throughout the review, series of stable organic compounds or transition metal complexes are numbered by arabic numerals and small letters, while reactive intermediates or transition states are designated by arabic numerals followed by capital letters. 

Nevertheless, polymerizations other than the anionic ones have also been carried out using enolates as ligands of transition metal cations. Metal acetalyacetonates are indeed organometallic compounds that directly contributed to the control of radical polymerization, ring-opening polymerization and coordination polymerization of specific monomers, as discussed hereafter. 

Apparently, the reactivity of organometallic compounds in the addition of olefins to Mt—C bonds is determined by the capability of these compounds to coordinate olefins. The formation of intermediate n-complexes ensures further insertion of olefin by a concerted mechanism with a low activation energy. Thus, a high reactivity of active centers, containing a transition metal, comparable to the reactivity of the radical active centers, is achieved. The activation energy of the propagation in olefin polymerization on catalysts containing transition metals (2-6 kcal/mol) does not exceed its value for the radical polymerization (Table 10). 

---