Carbon reaction + metal atoms

These metallacycles have been prepared by additions to multiple bonds and substitutions at carbon or metal atoms, as well as by simple acid-base reactions. 

Intramolecular hydrogen migration between carbon and metal atoms is, of course, important to various catalytic reactions and may be sufficiently fast to give nmr coalescence. Treatment of compound 29 with D2O in CD3NO3 at... 

In the synthesis of molecules without functional groups the application of the usual polar synthetic reactions may be cumbersome, since the final elimination of hetero atoms can be difficult. Two solutions for this problem have been given in the previous sections, namely alkylation with nucleophilic carbanions and alkenylation with ylides. Another direct approach is to combine radical synthons in a non-polar reaction. Carbon radicals are. however, inherently short-lived and tend to undergo complex secondary reactions. Escheirmoser s principle (p. 34f) again provides a way out. If one connects both carbon atoms via a metal atom which (i) forms and stabilizes the carbon radicals and (ii) can be easily eliminated, the intermolecular reaction is made intramolecular, and good yields may be obtained. 

Oxidation can also occur at the central metal atom of the phthalocyanine system (2). Mn phthalocyanine, for example, can be produced ia these different oxidation states, depending on the solvent (2,31,32). The carbon atom of the ring system and the central metal atom can be reduced (33), some reversibly, eg, ia vattiag (34—41). Phthalocyanine compounds exhibit favorable catalytic properties which makes them interesting for appHcations ia dehydrogenation, oxidation, electrocatalysis, gas-phase reactions, and fuel cells (qv) (1,2,42—49). 

The bonding between carbon monoxide and transition-metal atoms is particularly important because transition metals, whether deposited on soHd supports or present as discrete complexes, are required as catalysts for the reaction between carbon monoxide and most organic molecules. A metal—carbon ( -bond forms by overlapping of metal orbitals with orbitals on carbon. Multiple-bond character between the metal and carbon occurs through formation of a metal-to-CO TT-bond by overlap of metal-i -TT orbitals with empty antibonding orbitals of carbon monoxide (Fig. 1). 

If the reaction temperature is raised to 430 K and the carbon monoxide pressure to 3 atm, coordination of the metal atom in the rearranged product occurs via the phosphorus site, as in 159 (M = Cr, Mo, W) [84JOM(263)55]. Along with this product (M = W) at 420 K, formation of the dimer of 5-phenyl-3,4-dimethyl-2//-phosphole, 160 (the a complex), is possible as a consequence of [4 - - 2] cycloaddition reactions. Chromium hexacarbonyl in turn forms phospholido-bridged TiyP)-coordinatedcomplex 161. At 420 K in excess 2,3-dimethylbutadiene, a transformation 162 163 takes place (82JA4484). 

The interstitial carbides are compounds formed by the direct reaction of a d-block metal and carbon at temperatures above 2000°C. In these compounds, the C atoms occupy the gaps between the metal atoms, as do the H atoms in metallic hydrides (see Fig. 14.9). Here, however, the C atoms pin the metal atoms together into a rigid structure, resulting in very hard substances with melting points often well above 3000°C. Tungsten carbide, WC, is used for the cutting surfaces of drills, and iron carbide, FesC, is an important component of steel. 

Dihydro-lH-l,5,2-azasilaboroles derive from the 2,5-dihydro-lH-l,2-aza-boroles ( 6.5.3.3) by substitution of the carbon neighboring N by a silicon atom. They may act as four-electron donors using electron density from the C=C double bond and the N atom. The B atom behaves as an acceptor center. Two pathways are known for complex synthesis reaction with a generated transition-metal complex fragment and reaction with metal atoms by the metal-vapor synthesis method. 

With respect to the thermodynamic stability of metal clusters, there is a plethora of results which support the spherical Jellium model for the alkalis as well as for other metals, like copper. This appears to be the case for cluster reactivity, at least for etching reactions, where electronic structure dominates reactivity and minor anomalies are attributable to geometric influence. These cases, however, illustrate a situation where significant addition or diminution of valence electron density occurs via loss or gain of metal atoms. A small molecule, like carbon monoxide,... 

Co-condensation of transition metal atoms with arenes such as benzene and toluene is well known to yield bis-arene-metal compounds. However, in many cases the yields based on the metal atoms are less than 40%. Evidence that competing reactions such as carbon-hydrogen activation can occur is provided by the isolation of non-metal-containing products such as biaryl derivatives (2JL). ... 

Among the transfer and exchange of non-metals, the reactions of atomic oxygen, O, at low potential are unusual in that transport is not required. H20 carries O everywhere but it is not by itself active in O-incorporation into carbon frameworks. It is observed that fixed Mo (W) coenzymes have always been used as catalysts in the oxygen atom transfer from H20 to aldehydes reversibly. 

Redox reactions are considered as being able to provide versatile and efficient methods for bringing about ring transformations. Transition metal complexes in particular are able to induce or catalyze oxidative or reductive transformations of small ring compounds. Organometallics, such as metal-lacycles derived by the insertion of metal atoms into rings, are involved as key intermediates in many cases, allowing subsequent functionalization or carbon-carbon bond formation. 

For over 15 years we have conducted research utilizing metal atoms in low temperature spectroscopic and synthetic studies at Rice University.8 Our synthetic work was started in the late 1960s with the work of Krishnan, on lithium atom reactions with carbon monoxide, extended by Meier- in his studies of lithium atom reactions with water and ammonia and expanded over the next several years to include metal atom interactions with HF, H2O, H3N, H4C, and their hundreds of organic analogs—RF, R2O, ROH, R3N,. . . H3N, R4C, R3CH, etc. A most exciting aspect of... 

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