Reactivity organometallics

P. Hofmann, Organometallic Reactivity and Applied Quantum Chemistry - Some Aspects of CH Activation, in Organometallics in Organic Synthesis, (A. deMeijere, H. tomDieck, Edits.), p.l ff, Springer, Berlin, 1987 see also [5]. 

With a greater understanding of the chemistry and mechanism of stoichiometric organometallic reactivity inside of 1, catalytic systems were investigated. The prevalence of monocationic rhodium catalysts in the literature, and the water solubility of... 

In this book we are not concerned with organometallic reactivity of compounds containing M-C bonds, and so to all intents and purposes this section is about the reactions of nitriles or cyanides with nucleophiles. Reactions of co-ordinated alkynes are adequately discussed elsewhere. 

An area of experimental investigation that has not received much attention is the determination of basic thermodynamic data for substituted metallocenes (i.e., bond and vaporization enthalpies). Considering how important these values can be in the prediction and interpretation of reaction mechanisms in organometallic reactivity,195 it is surprising that more data are not available. One would expect this to change in the future. 

The chemistry of ruthenium (II) complexes incorporating P-donor ligands, particularly phosphines and diphosphines, is flourishing. This class of compounds has given rise to a versatile organometallic reactivity. They are also found in many catalytic cycles, but decoordination of the phosphine from the coordination sphere of the metal is often required for the catalysis to proceed. 

The ionization potential in a simple one-electron approximation measures the energy of the highest occupied molecular orbital (HOMO). This orbital is only one of an entire manifold of levels which contribute to the bonding characteristics and total stability of the cluster. Frontier fragment-orbital analysis in organometallic reactivity studies has provided a clear indication... 

With regard to organometallic reactivity, little is known on the various SCFs. Even carbon dioxide can be reactive if it inserts in M-H, M-R, M-OR, or M-NR2 bonds. In this case, SCCO2 can be used simultaneously as C, building block. 

Organometallics Reactive If Large Electronegativity Difference, Metai Hydrides NaH and KH Are Bases, AIH4 and BH4 Are Good Nucleophiles... 

Convenient Pressure Reactors for Organometallic Reactivity Studies... 

Metal Effects on Metal carbonyl Reactivity. The effect of the metal center on organometallic reactivity is not as clearly defined as for coordination complexes. We will examine (a) the effect of charge, (b) first-row, second-row, and third-row effects and (c) the effect of d-electron count. As will be discussed in Section 4.1, the enhanced reactivity of odd-electron complexes is a major effect of the metal center. 

The second case study we wish to describe concerns the photochemistry of Fe(CO)s. How spin states affect organometallic reactivity is a fundamental question that is key to many areas of inorganic chemistry, and Fe(CO)s is a... 

Hindson K, de Bruin B (2012) Cooperative redox non-innocent ligands in directing organometallic reactivity (Eur. J. Inorg. Chem. 3/2012). Eur J Inorg Chem 2012 340-342... 

Iodomethylzinc iodide breaks the pattern we have seen so far in organometallic reactivity. Unlike organolithium, Grignard, and organocopper reagents, all of which are nucleophilic, iodomethylzinc iodide is electrophilic. 

The second important type of organometallic reactivity of B 12-derivatives concerns the highly nucleophilic/nucleofugal Co(I)-corrins [75,91,132[. These provide the basis of the heterolytic mode of formation/cleavage of the Co - C bond, important in methyl-corrinoids in enzyme-catalyzed methyl-transfer reactions [125-127]. This mode is represented by the reaction of Co(I)-corrins with alkylating agents in the formation of the Co - CH3 bond and the nucleophile-induced demethylation of methyl Co(III)-corrins for the... 

In a catalytic cycle of B -dependent methyl transferases the corrinoid is indicated to cycle between a methyl-Co(III)-corrin and a Co(I)-corrin [125,126, 153,155]. The changing between the hexacoordinate methyl-Co(III)-form and (presumably) tetracoordinate Co(I)-form is accompanied by constitu-tional/conformational changes, which are highly likely to provide a means for controlling the organometallic reactivity of the bound cofactor [170], sub-... 

Much of the organometallic reactivity of late-metal-amido complexes is presented in later chapters of this text. In general, these complexes are reactive toward many classic organometallic processes, such as reductive elimination, migratory insertion, and 3-hydrogen... 

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