Metal carbonyl derivatives, containing

Several examples of the use of hexamethyldistannoxane as a Me3Sn group transfer agent are reported. Thus the dimetallic carbonyl dimers of Mo, Mn, Fe, Co, and Ni react with Me3SnOSnMe3 [and also with tris(trimethylstannyl)amine, N(SnMe3)3] to form metal-carbonyl derivatives containing tin complexes (equation 118)277. 

METAL CARBONYL DERIVATIVES CONTAINING PHOSPHORUS DONOR LIGANDS... 

The latter contains very long Ir-Ir bonds (3.086 A), suggesting very weak, if any, metal-metal interactions. Further studies on metal carbonyl derivatives containing or Te ° have been described. These include details of... 

The first borane-metal carbonyl derivatives contain the rather unstable anions [Re(CO)5(BH3)]-, [Re(COs)(BH3)2]-, and [Mn(C05)BH3]-, and a somewhat more stable species is [Mn(CO)4(BH3)P(C6Hs)3]. The increased stability of the phosphine-substituted borane complex suggests a role for the phosphine primarily as a a donor, as also indicated by the NMR spectrum of [Mn(CO)4P(C6H5)3] (371). An interesting series of metal derivatives of... 

Studies on various derivatives of ferrocene, cymantrene, benzene-chromium tricarbonyl, and butadieneiron tricarbonyl were recently reported (174, 176). Carbonyl derivatives containing the COR group lose CO to give an ion probably containing the R group attached to the metal, e.g. 

Following these, this method has been widely used Table IV lists more recent applications. Only those reactions that evolve dihydrogen are included here. Oxidative addition reactions leading to metal hydride derivatives are included in Table V, while processes involving elimination of dihydrogen between hydridosilanes and metal hydride derivatives containing no carbonyl groups are deferred until Section H,G,1. 

I n this chapter we include the first compilation of reported absolute intensity data for metal carbonyl species. We have attempted to refer this data to a common set of units but the literature contains ambiguities which it has not always proved possible to resolve. Absolute intensity data such as these provide an indication of the extent to which the vibrations of a metal carbonyl derivative are affected by the solvent in which they are studied. Present indications are that solvent-solute interactions are of prime importance and it would be most useful to have gas-phase absolute intensity data with which to compare solution measurements. 

D. Pd-CATALYZED CROSS-COUPLING OF a,jS-UNSATURATED CARBONYL DERIVATIVES CONTAINING a-HALOGEN OR a-METAL GROUPS... 

Because transition-metal carbonyls react with Zn, Cd and Hg to form compounds containing metal-mctal bonds (see 8.3.3.4), the derivatives can be prepared by combining reactants under carbonyl-forming conditions ... 

Rhin(bpy)3]3+ and its derivatives are able to reduce selectively NAD+ to 1,4-NADH in aqueous buffer.48-50 It is likely that a rhodium-hydride intermediate, e.g., [Rhni(bpy)2(H20)(H)]2+, acts as a hydride transfer agent in this catalytic process. This system has been coupled internally to the enzymatic reduction of carbonyl compounds using an alcohol dehydrogenase (HLADH) as an NADH-dependent enzyme (Scheme 4). The [Rhin(bpy)3]3+ derivative containing 2,2 -bipyridine-5-sulfonic acid as ligand gave the best results in terms of turnover number (46 turnovers for the metal catalyst, 101 for the cofactor), but was handicapped by slow reaction kinetics, with a maximum of five turnovers per day.50... 

The complexes appear to be based on a tetrahedral distribution of metal atoms, with the di- and triosmium derivatives containing no bridging carbonyl group. A detailed X-ray structure of the complex H3CoOs3(CO)12 has been carried out (249). 

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