Covalent bonds, oxidative addition

Palladium(0)-catalyzed transformations generally involve three steps oxidative addition, insertion or transmetallation (really a special type of insertion), and reductive elimination. Together they comprise a pathway for the formation of new carbon-carbon bonds. Oxidative addition takes place when a coordinatively unsaturated Pd(0) species cleaves a covalent bond to give a new complex in which die palladium is oxidized to Pd(II). Typically dissociation of two phosphine ligands to a 14-electron complex is file first step followed by oxidative addition to give a 16-electron Pd(II) complex. 

The oxidation of OH by [Fe(CN)6] in solution has been examined. Application of an electrical potential drives the reaction electrochemically, rather than merely generating a local concentration of OH at the anode, as has been suggested previously, to produce both O and [Fe(CN)6] in the vicinity of the same electrode. With high [OH ] or [Fe(CN)6] /[Fe(CN)6] ratio, the reaction proceeds spontaneously with a second-order rate constant of 2.2 x 10 M s at 25 °C. Under anaerobic conditions, iron(III) porphyrin complexes in dimethyl sulfoxide solution are reduced to the iron(II) state by addition of hydroxide ion or alkoxide ions. Excess hydroxide ion serves to generate the hydroxoiron(II) complex. The oxidation of hydroxide and phenoxide ions in acetonitrile has been characterized electrochemically " in the presence of transition metal complexes [Mn(II)L] [M = Fe,Mn,Co,Ni L = (OPPh2)4,(bipy)3] and metalloporphyrins, M(por) [M = Mn(III), Fe(III), Co(II) por = 5,10,15,20-tetraphenylpor-phinato(2-), 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphinato(2-)]. Shifts to less positive potentials for OH and PhO are suggested to be due to the stabilization of the oxy radical products (OH and PhO ) via a covalent bond. Oxidation is facilitated by an ECE mechanism when OH is in excess. 

The major synthetic routes to transition metal silyls fall into four main classes (1) salt elimination, (2) the mercurial route, a modification of (1), (3) elimination of a covalent molecule (Hj, HHal, or RjNH), and (4) oxidative addition or elimination. Additionally, (5) there are syntheses from Si—M precursors. Reactions (1), (2), and (4), but not (3), have precedence in C—M chemistry. Insertion reactions of Si(II) species (silylenes) have not yet been used to form Si—M bonds, although work may be stimulated by recent reports of MejSi 147) and FjSi (185). A new development has been the use of a strained silicon heterocycle as starting material (Section II,E,4). 

If R can react with itself or additional components (R contains vinyl, methacryl or epoxy groups, for example), the result of the condensation process is a flexible network of inorganic oxide covalently bonded to organic polymers, namely a hybrid nanocomposite lacking interface imperfections. The properties of this hybrid nanocomposite are intermediate between those of polymers and glasses, and can meet unique requirements. 

During the chemisorptions of Ru3(CO)i2 or Os3(CO)i2 on silica, the first step with the surface silanols was to produce a covalent bonding with the silica surface by oxidative addition of the silanol group to the metal-metal bond of the clusters. The nature of surface molecular species [=Si-0)(M3( x-H)(CO)io)j covalently linked to the silica surface (M = Ru, Os) was clearly defined and structurally characterized by a series of physical and chemical techniques, including mass balance taking into account the evolution of two molecules of CO and one molecule of hydrogen [27, 33, 35]. 

A. 1.1. Covalently Functionalized Dendrimers Applied in a CFMR The palladium-catalyzed allylic substitution reaction has been investigated extensively in the preceding decades and provides an important tool for the formation of carbon—carbon and carbon—heteroatom bonds 14). The product is formed after attack of a nucleophile to an (f/ -allyl)Pd(II) species, formed by oxidative addition of the unsaturated substrate to palladium(0) (Scheme 1). To date several nucleophiles have been used, mostly resulting in the formation of carbon—carbon and... 

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