Coordination compounds oxidative addition

This reaction is a variation of the hydroformylation reaction. Transmetallation of Rh(I)(acac) with the alkylmercury(I) compound gives ClHg(acac) and an alkylrhodium(I) compound. Oxidative addition of H2 gives a Rh(III) compound, and coordination and insertion of CO gives the acylrhodium(IH) compound. Reductive elimination then gives the product and regenerates Rh(I) — but as a Rh-H, not as Rh(acac). 

Addition of anionic Fischer carbene complexes, of their CS2 adducts and of an anionic thiocarbyne complex to cationic organometallic Lewis acids and to coordinated, unsaturated hydrocarbons gives novel hydrocarbon bridged heterodimetallic compounds. Oxidative addition of halocarbyne complexes to zerovalent platinum and palladium complexes provides a synthesis of carbido bridged complexes. 

Formation of a Tr-allylpalladium complex 29 takes place by the oxidative addition of allylic compounds, typically allylic esters, to Pd(0). The rr-allylpal-ladium complex is a resonance form of ir-allylpalladium and a coordinated tt-bond. TT-Allylpalladium complex formation involves inversion of stereochemistry, and the attack of the soft carbon nucleophile on the 7r-allylpalladium complex is also inversion, resulting in overall retention of the stereochemistry. On the other hand, the attack of hard carbon nucleophiles is retention, and hence Overall inversion takes place by the reaction of the hard carbon nucleophiles. 

TT-Aliylpalladium chloride reacts with a soft carbon nucleophile such as mal-onate and acetoacetate in DMSO as a coordinating solvent, and facile carbon-carbon bond formation takes place[l2,265], This reaction constitutes the basis of both stoichiometric and catalytic 7r-allylpalladium chemistry. Depending on the way in which 7r-allylpalladium complexes are prepared, the reaction becomes stoichiometric or catalytic. Preparation of the 7r-allylpalladium complexes 298 by the oxidative addition of Pd(0) to various allylic compounds (esters, carbonates etc.), and their reactions with nucleophiles, are catalytic, because Pd(0) is regenerated after the reaction with the nucleophile, and reacts again with allylic compounds. These catalytic reactions are treated in Chapter 4, Section 2. On the other hand, the preparation of the 7r-allyl complexes 299 from alkenes requires Pd(II) salts. The subsequent reaction with the nucleophile forms Pd(0). The whole process consumes Pd(ll), and ends as a stoichiometric process, because the in situ reoxidation of Pd(0) is hardly attainable. These stoichiometric reactions are treated in this section. 

Polymerization of olefins such as styrene is promoted by acid or base or sodium catalysts, and polyethylene is made with homogeneous peroxides. Condensation polymerization is catalyzed by acid-type catalysts such as metal oxides and sulfonic acids. Addition polymerization is used mainly for olefins, diolefins, and some carbonyl compounds. For these processes, initiators are coordination compounds such as Ziegler-type catalysts, of which halides of transition metals Ti, V, Mo, and W are important examples. 

This index contains over 25 000 entries to the 6562 text pages of Volumes 1-6. The index covers general types of coordination complex, specific coordination complexes, general and specific organic compounds where their synthesis or use involves coordination complexes, types of reaction (insertion, oxidative addition, etc.), spectroscopic techniques (NMR, IR, etc.), and other topics involving coordination complexes, such as medicinal and industrial applications. 

Finally, new tricyclic hexacoordinated phosphoranes with internal P-N coordination were synthesized by Swamy and coworkers by oxidative addition of cyclic phosphite precursors with quinones or with a combination of diols and (z-Pr)2NCl [57, 58]. Various ring sizes from five to eight membered were obtained showing the generality of the approach. A selection of compounds (47a-47e) is presented in Fig. 8. 

Bivalent tin compounds can easily be transformed to fourvalent tin compounds by oxidizing agents. Mechanistically, this reaction can be understood as an insertion of a six-electron system into a two-electron bond, resulting in a tetrahedrally tetra-coordinated tin atom. This process is often also regarded as an oxidative addition, a distinction being made between additions to a-bonds and to it-bonds. 

The five-coordinate complexes Ir(CO)(PPh3)2L, where HL = /3-diketone, A-benzoyl-A-phenyl-hydroxylamine, salicylaldehyde, 8-hydroxyquinoline, 2-hydroxybenzophenone, 2-hydroxy-8-methoxybenzophenone, were prepared from [Ir(CO)(PPh3)2Cl].632 The resulting compounds all underwent oxidative addition reactions with Br2. Reaction of [(cod)2IrCl]2 with N-substituted 3-hydroxy-2-methyl-4-pyridine gives the bichelated complex (389). 33... 

The study of [4.4.0] ring systems has resulted primarily from the study of various other aspects of phosphorus chemistry. An investigation into the effect of nitrogen donor action on the increase in coordination at phosphorus in a series of oxyphosphoranes led Holmes and co-workers <1998IC4945> to compounds 24 and 25. The compounds were fully characterized by NMR spectroscopy and X-ray diffraction. Compound 24 was heated for 30 min at 140°C in an NMR tube. The reaction was followed by 31P NMR spectroscopy which indicated that conversion to a phosphorane 26 and a small amount of phosphate had taken place (Equation 4). The pentaoxyphosphorane 25 was successfully produced via an oxidative addition reaction between the diol 27 and triphenyl phosphate in the presence... 

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