Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence

Efficient and reliable amplification of chirality has borne its greatest fruit with transition metal-catalyzed reactions since enantiocontrol may often be imposed by replacing an achiral or chiral racemic ligand with one that is chiral and scalemic While the most thoroughly developed enantioselective transition metal-catalyzed reactions are those involving transfer of oxygen (epoxidation and dihydroxylation)1,2 and molecular hydrogen,3 the focus of this review is on the area of enantioselective transition metal-catalyzed allylic alkylations which may involve C-C as well as C-X (X ) H or heteroatom) bond formation4-9 The synthetic utility of transitionmetal-catalyzed allylic alkylations has been soundly demonstrated since its introduction nearly three decades ago10-21 In contrast to processes where the allyl moiety acts as the nucleophilic partner, we will limit our discussion to processes which result in nucleophilic displacements on allylic substrates (eq 1) Such reactions have been recorded with a broad

http://web4.uwindsor.ca/users/j/jlichaa/reference.nsf/0/10ff8b04ff3a317885256d88005720f6/$FILE/cr-1996-96-395-allylpd-asym.pdf

Asymmetric Transition Metal-Catalyzed Allylic Alkylations.

ion. The oxidative addition mechanism was originally proposed22i because of the lack of a strong rate dependence on polar factors and on the acidity of the medium. Later, however, the electrophilic substitution mechanism also was proposed. Recently, the oxidative addition mechanism was confirmed by investigations into the decomposition and protonolysis of alkylplatinum complexes, which are the reverse of alkane activation. There are two routes which operate in the decomposition of the dimethylplatinum(IV) complex Cs2Pt(CH3)2Cl4. The first route leads to chloride-induced reductive elimination and produces methyl chloride and methane. The second route leads to the formation of ethane. There is strong kinetic evidence that the ethane is produced by the decomposition of an ethylhydridoplatinum(IV) complex formed from the initial dimethylplatinum(IV) complex. In D2O-DCl, the ethane which is formed contains several D atoms and has practically the same multiple exchange parameter and distribution as does an ethane which has undergone platinum(II)-catalyzed H-D exchange with D2O. Moreover, ethyl chloride is formed competitively with H-D exchange in the presence of platinum(IV). From the principle of microscopic reversibility it follows that the same ethylhydridoplatinum(IV) complex is the intermediate in the reaction of ethane with platinum(II). Important results were obtained by Labinger and Bercaw62c in the investigation of the protonolysis mechanism of several alkylplatinum(II) complexes at low temperatures. These reactions are important because they could model the microscopic reverse of C-H activation by platinum(II) complexes. Alkylhydridoplatinum(IV) complexes were observed as intermediates in certain cases, such as when the complex (tmeda)Pt(CH2Ph)Cl or (tmeda)PtMe2 (tmeda ) N,N,N′,N′-tetramethylenediamine) was treated with HCl in CD2Cl2 or CD3OD, respectively. In some cases H-D exchange took place between the methyl groups on platinum and the, CD3OD prior to methane loss. On the basis of the kinetic results, a common mechanism was proposed to operate in all the reactions: (1) protonation of Pt(II) to generate an alkylhydridoplatinum(IV) intermediate, (2) dissociation of solvent or chloride to generate a cationic, fivecoordinate platinum(IV) species, (3) reductive C-H bond formation, producing a platinum(II) alkane σ-complex, and (4) loss of the alkane either through an associative or dissociative substitution pathway. These results implicate the presence of both alkane σ-complexes and alkylhydridoplatinum(IV) complexes as intermediates in the Pt(II)-induced C-H activation reactions. Thus, the first step in the alkane activation reaction is formation of a σ-complex with the alkane, which then undergoes oxidative addition to produce an alkylhydrido complex. Reversible interconversion of these intermediates, together with reversible deprotonation of the alkylhydridoplatinum(IV) complexes, leads to multiple H-D exchange

Activation of c-h bonds by metal complexes

The selective transformation of ubiquitous but inert C–H bonds to other functional groups has far-reaching practical implications, ranging from more efficient strategies for fine chemical synthesis to the replacement of current petrochemical feedstocks by less expensive and more readily available alkanes. The past twenty years have seen many examples of C–H bond activation at transition-metal centres, often under remarkably mild conditions and with high selectivity. Although profitable practical applications have not yet been developed, our understanding of how these organometallic reactions occur, and what their inherent advantages and limitations for practical alkane conversion are, has progressed considerably. In fact, the recent development of promising catalytic systems highlights the potential of organometallic chemistry for useful C–H bond activation strategies that will ultimately allow us to exploit Earth's alkane resources more efficiently and cleanly.

Understanding and exploiting C–H bond activation

▪ Abstract Proton-coupled electron transfer (PCET) is an important mechanism for charge transfer in a wide variety of systems including biology- and materials-oriented venues. We review several are...

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Proton-Coupled Electron Transfer

Asymmetric hydrogenation of methyl (Z)-.alpha.-acetamidocinnamate catalyzed by [1,2-bis(phenyl-o-anisoyl)phosphino)ethane]rhodium(I): kinetics, mechanism and origin of enantioselection

Coenzyme B12 serves as a cofactor in various enzymatic reactions in which a hydrogen atom is interchanged with a substituent on an adjacent carbon atom. Measurement of the dissociation energy of the coenzyme's cobalt-carbon bond and studies of the rearrangement of model free radicals related to those derived from methylmalonyl-coenzyme A suggest that these enzymatic reactions occur through homolytic dissociation of the coenzyme's cobalt-carbon bond, abstraction of a hydrogen atom from the substrate by the coenzyme-derived 5'-deoxyadenosyl radical, and rearrangement of the resulting substrate radical. The only role thus far identified for coenzyme B12 in these reactions--namely, that of a free radical precursor--reflects the weakness, and facile dissociation, of the cobalt-carbon bond.

http://science.sciencemag.org/content/sci/227/4689/869.full.pdf

Mechanisms of coenzyme B12-dependent rearrangements.

Rhodium complexes containing chiral phosphine ligands catalyze the hydrogenation of olefinic substrates such as alpha-aminoacrylic acid derivatives, producing chiral products with very high optical yields. Elucidation of the mechanisms of such reactions leads to the conclusion that the stereoselection is dictated not by the preferred initial binding of the substrate to the chiral catalyst, but rather by the much higher reactivity of the minor diastereomer of the catalyst-substrate adduct corresponding to the less favored binding mode.

https://science.sciencemag.org/content/sci/217/4558/401.full.pdf

Mechanism and stereoselectivity of asymmetric hydrogenation.

Assessment of the T1 criterion for distinguishing between classical and nonclassical transition-metal hydrides : hydride relaxation rates in tris(triarylphosphine)osmium tetrahydrides and related polyhydrides

Jack Halpern

Papers

Asymmetric hydrogenation of methyl (Z)-.alpha.-acetamidocinnamate catalyzed by [1,2-bis(phenyl-o-anisoyl)phosphino)ethane]rhodium(I): kinetics, mechanism and origin of enantioselection

Mechanisms of coenzyme B12-dependent rearrangements.

Mechanism and stereoselectivity of asymmetric hydrogenation.

Assessment of the T1 criterion for distinguishing between classical and nonclassical transition-metal hydrides : hydride relaxation rates in tris(triarylphosphine)osmium tetrahydrides and related polyhydrides

Identification of the enantioselective step in the asymmetric catalytic hydrogenation of a prochiral olefin