Metal carbonyl complexes reactions with

Metal carbonyls undergo reactions with a great many compounds to produce mixed carbonyl complexes. A large number of these reactions involve the replacement of one or more carbonyl groups by a substitution reaction. Such reactions have also been studied kinetically in some cases. 

The reaction of the transition-metal fragments with main group 15 elements directly has proven a very fruitful field for exploration. The methodology has been successful for a wide range of metal complexes. These fall generally into three basic types (1) reactions with cyclopentadienyl metal carbonyls, (2) reactions with homoleptic metal carbonyls and substituted derivatives, and (3) reactions with metal cations in the presence of a multi-dentate chelating ligand. 

Conjugated dienes, upon complexation with metal carbonyl complexes, are activated for Friedel-Crafts acylation reaction at the akyhc position. Such reactions are increasingly being used in the stereoselective synthesis of acylated dienes. Friedel-Crafts acetylation of... 

It has been observed, however, that the enantioselectivity of reactions of tartrate ester modified allylboronates with metal carbonyl complexes of unsaturated aldehydes are significantly improved compared with the results with the metal-free, uncomplexed aldehydes72. Two such examples involve the (benzaldehyde)tricarbonylchromium complex and the hexacarbonyl(2-... 

The reactions of nucleophilic reagents with cationic and uncharged metal carbonyl complexes have received much attention in the past, and it is not surprising that these studies have now been extended to isocyanide metal complexes. Different products in these reactions can arise by three general routes these include ligand substitution, reactions involving attack at a ligand, and reduction of the metal complex. All have been observed in reactions with metal isocyanide complexes. 

Base catalysis of ligand substitutional processes of metal carbonyl complexes in the presence of oxygen donor bases may be apportioned into two distinct classifications. The first category of reactions involves nucleophilic addition of oxygen bases at the carbon center in metal carbonyls with subsequent oxidation of CO to C02, eqns. 1 and 2 (l, 2). Secondly, there are... 

The reactivity of these metal hydride-metal carbonyl reactions can be correlated with the nature of the reactants in a manner consistent with the proposed mechanism nucleophilic attack by hydride on coordinated CO. Thus reactions involving the highly nucleophilic group IV hydride, Cp gZrHg, are much faster than those of group V metal hydrides. On the other hand, the relatively electrophilic neutral binary metal carbonyls all react with Cp2NbH under mild conditions (20-50° C), whereas more electron-rich complexes such as cyclopentadienylmetal carbonyls (Cp2NbH(C0), CpV(CO) ) or anionic carbonyls (V(CO)g ) show no reaction under these conditions. 

Low-valent clusters [RM]X are valuable starting reagents for various oxidation reactions as will be shown in the following for the tetrahedral cluster [TMS3CM]4 (M = Ga 383, In 384). (Reactions with metal carbonyl complexes,... 

Supercritical fluids allow the formation of species that cannot be made in conventional solvents. For example, rj2-H2 complexes have been generated by direct reaction of hydrogen with a transition metal carbonyl complex [10]. In order to isolate these compounds, a continuous flow reactor was used and such compounds could be isolated with surprising ease. 

Reaction of (butadiene)ZrCp2 (31/32), and substituted Cp variants, with a wide range of metal-carbonyl complexes, generates the chelated metal-carbene complexes 163 (equation 22)163. The crystal structure of a number of these complexes has been determined... 

Cationic mononuclear metal complexes, reaction with anionic carbonyl clusters, 30 155-158... 

---