O-Alkyl complexes

Transformation of the. r-olefin complex 7 to a o -alkyl complex 7a via insertion of the olefin into the metal-hydride bond (step 3) ... 

Mechanism of Homogeneously Catalyzed Hydrosilylation. A mechanism analogous to the homogeneous hydrogenation reaction has been proposed by Chalk and Harrod (200) (Scheme 47) for the platinum catalyzed hydrosilylation. In the first step, oxidative addition of the silane occurs and leads to an hexa-coordinate intermediate complex 126, in which both silane and olefin are cis oriented. Hydrogen migration produces a o-alkyl complex 127 from which the hydrosilylation products 128 are obtained by reductive elimination. 

It should be noted that complexes of types VII-5 or VII-7 can be easily prepared by the method initially described in [30a-d], The chloride complex Pt"Cl4 - reacts at room temperature in aqueous solution with alkyl iodide to produce a o-alkyl complex of platinum(IV). Methyl [30a], ethyl [30b,c], and acetonyl [30d] complexes of Pt(IV) have been prepared by this method. An interesting feature of the reaction is that the sixth coordination site in the octahedral molecule of the product is occupied by water, while the T ion is bound to another molecule of the platinum(II) complex (Ptlj and analogous products are formed and precipitate) ... 

Nucleophilic attack of hydride on a cationic olefin complex gives a o-alkyl complex. Fe retains die oxidation state +2. 

Kurosawa has shown that the related palladium(II) olefin complex [( ti -C5H5)Pd(Ph3P) (CHj=CHj)] undergoes clean trans attack by both methoxide and the anion of acety-lacetone. These examples of additions to iron- and palladium-olefin complexes occur by attack only at the ligand and lead to stable o-alkyl products because the metal center is coordinatively saturated. This coordinative saturation disfavors attack at the metal that would lead to either products from syn addition or displacement of the olefin. The cr-alkyl complexes that are products of these examples of nucleophilic attack are stable because the most common mode for decomposition of o-alkyl complexes, 3-hydrogen elimination, requires the presence of a vacant coordination site cis to the alkyl group, as noted in Chapters 8 and 9. Such a site is not present in these cr-alkyl products. 

Catalysts used in the polymerization of C-5 diolefins and olefins, and monovinyl aromatic monomers, foUow closely with the systems used in the synthesis of aHphatic resins. Typical catalyst systems are AlCl, AIBr., AlCl —HCl—o-xylene complexes and sludges obtained from the Friedel-Crafts alkylation of benzene. Boron trifluoride and its complexes, as weU as TiCl and SnCl, have been found to result in lower yields and higher oligomer content in C-5 and aromatic modified C-5 polymerizations. 

Caprolactam is an amide and, therefore, undergoes the reactions of this class of compounds. It can be hydrolyzed, Ai-alkylated, O-alkylated, nitrosated, halogenated, and subjected to many other reactions (3). Caprolactam is readily converted to high molecular weight, linear nylon-6 polymers. Through a complex series of reactions, caprolactam can be converted to the biologically and nutritionally essential amino acid L-lysine (10) (see Amino acids). 

Manufacture of alkylsulfones, important intermediates for metal-complex dyes and for reactive dyes, also depends on O-alkylation. An arylsulphinic acid in an aqueous alkaline medium is treated with an alkylating agent, eg, alkyl haUde or sulfate, by a procedure similar to that used for phenols. In the special case of P-hydroxyethylsulfones (precursors to vinylsulfone reactive dyes) the alkylating agent is ethylene oxide or ethylene chlorohydrin. 

Chromium carbene complexes like 13, which are called Fischer carbene complexes, can conveniently be prepared from chromium hexacarbonyl 11 and an organolithium compound 12, followed by an O-alkylation step ... 

H NMR spectroscopy studies of iron(IIl) a-alkyl and o-aryl porphyrins have been very important in elucidating spin states. Alkyl and most aryl complexes with simple porphyrin ligands (OEP, TPP, or TTP) are low spin, S — I /2 species. NMR spectra for the tetraarylporphyrin derivatives show upheld resonances for the porphyrin pyrrole protons (ca. — 18 to —35 ppm), and alternating upfield and downfield hyperfine shifts for the axial alkyl or aryl resonances. For -alkyl complexes, the a-protons show dramatic downfield shifts (to ca. 600 ppm), upfield shifts for the /3-protons (—25 to — 160 ppm) and downfield shifts for the y-protons (12 ppm). The cr-protons of alkyliron porphyrins are not usually detected as a result of their large downfield shift and broad resonance. These protons were first detected by deuterium NMR in the dcuterated complexes Fe(TPP)CD3 (532 ppm) and Fe(TPP)CD2CDi (562, -117 ppm). ... 

The alkyl complexes [TpBut]MgR (R = Me, Et, Pr , Bul) react with excess 02 at room temperature to give alkylperoxo complexes [TpBut]-MgOOR (Scheme 5), which have been characterized by 170 NMR spectroscopy. Each complex exhibits two 170 NMR resonances in the ranges 8 102-183 and 8 323-427 for the two distinct oxygen atoms of the alkylperoxo (Mg-O-O-R) moiety (Table IV). Organometallic derivatives generally react with oxygen to produce complex mixtures (69,... 

Monoanions derived from nitroalkanes are more prone to alkylate on oxygen rather than on carbon in reactions with alkyl halides, as discussed in Section 5.1. Methods to circumvent O-alkylation of nitro compounds are presented in Sections 5.1 and 5.4, in which alkylation of the a.a-dianions of primary nitro compounds and radial reactions are described. Palladium-catalyzed alkylation of nitro compounds offers another useful method for C-alkylation of nitro compounds. Tsuj i and Trost have developed the carbon-carbon bond forming reactions using 7t-allyl Pd complexes. Various nucleophiles such as the anions derived from diethyl malonate or ethyl acetoacetate are employed for this transformation, as shown in Scheme 5.7. This process is now one of the most important tools for synthesis of complex compounds.6811-1 Nitro compounds can participate in palladium-catalyzed alkylation, both as alkylating agents (see Section 7.1.2) and nucleophiles. This section summarizes the C-alkylation of nitro compounds using transition metals. 

Methods for the preparation of tris(0-ethyl dithiocarbonato) complexes of chromium(III), indium(III), and cobalt(III) are presented and serve to illustrate procedures applicable to the preparation of O-alkyl dithiocarbonato, alkyl trithiocarbonato, iV,A7-dialkyldithiocarbamato, and 0,0 -dialkyl dithiophosphato complexes of several metals. 

It is necessary for the intermediate cation or complex to bear considerable car-bocationic character at the carbon center in order for effective hydride transfer to be possible. By carbocationic character it is meant that there must be a substantial deficiency of electron density at carbon or reduction will not occur. For example, the sesquixanthydryl cation l,26 dioxolenium ion 2,27 boron-complexed imines 3, and O-alkylated amide 4,28 are apparently all too stable to receive hydride from organosilicon hydrides and are reportedly not reduced (although the behavior of 1 is in dispute29). This lack of reactivity by very stable cations toward organosilicon hydrides can enhance selectivity in ionic reductions. 

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