Metals carbonyl exchange

The reaction occurs well below the temperature at which most of the parent metal carbonyls exchange with free CO and so is a direct nucleophilic attack on coordinated CO, although it may alternatively proceed via a prior electron path. The resulting acyl anions can be isolated as their [R4N] " or [ (C6H5)3P 2N] salts but are reactive and are used directly in subsequent alkylations with organic halides, acetylenes, a-/i-unsaturated carbonyls and alkyloxonium salts to form organic condensation products or metal-carbene complexes. 

As seen from Table III, iron pentacarbonyl reacts satisfactorily in spite of its inertness towards carbon monoxide substitution under the normal conditions 189). In benzene at 80° C, however, Fe(CO)5 dissociates rapidly (190). The Fe(CO)4 generated displays a nucleophilic reactivity which should promote an A-type mechanism. In spite of the specificities discussed, Maitlis et al. 177) have proposed the following mechanism for the metal carbonyl exchange reactions. 

Carbonylation by CO Exchange. A few metal carbonyls can be prepared by exchange of CO molecules. The reaction of WCl and Fe(CO) in the presence of hydrogen under pressure in diethyl ether results in yields of W(CO) as high as 85% (114). The same reaction can be used to... 

Trends in reactivity for ligand-exchange reactions of octahedral metal carbonyls. G. R. Dobson, Acc. Chem. Res., 1976, 9, 300-306 (48). 

AT-heterocyclic carbenes show a pure donor nature. Comparing them to other monodentate ligands such as phosphines and amines on several metal-carbonyl complexes showed the significantly increased donor capacity relative to phosphines, even to trialkylphosphines, while the 7r-acceptor capability of the NHCs is in the order of those of nitriles and pyridine [29]. This was used to synthesize the metathesis catalysts discussed in the next section. Experimental evidence comes from the fact that it has been shown for several metals that an exchange of phosphines versus NHCs proceeds rapidly and without the need of an excess quantity of the NHC. X-ray structures of the NHC complexes show exceptionally long metal-carbon bonds indicating a different type of bond compared to the Schrock-type carbene double bond. As a result, the reactivity of these NHC complexes is also unique. They are relatively resistant towards an attack by nucleophiles and electrophiles at the divalent carbon atom. 

CO2MC] were obtained by metal exchange liom (he same ruthenium-dicobalt precursor and analogous functionalized (cyclopentadienyl)metal carbonyl Related reactions of the selenido-containing cluster RuCo2(/r rSe)... 

The several polymeric metal carbonyls studied have led to some surprisingly high yields [e.g., Fe3(CO),2 and Ruj(CO)j2 in Table IV] but to no substantiated mechanisms. The 17% yield of Fe3(CO),2 in neutron-irradiated Fe(CO)j was interpreted as a reaction of Fe(CO)4 with the Fe(CO)5, but no further evidence is available. The study of Mn2(CO),o has been fruitful (44, 46). The insensitivity of the parent yield MnMn(CO),o to heat indicates that the molecule is formed by a reaction quite early in the sequence, perhaps epithermal. The discovery (46) of a species which reacts rapidly with I2 and exchanges with IMn(CO)5 led to the conclusion that the Mn(CO)5 radical is produced prominently (4.5%) by nuclear reactions in the solid decacarbonyl. The availability of this labeled Mn(CO)5 has made possible several interesting observations about the exchange properties of this radical in the solid (45) and in solution (42). 

The induction of steric effects by the pore walls was first demonstrated with heterogeneous catalysts, prepared from metal carbonyl clusters such as Rh6(CO)16, Ru3(CO)12, or Ir4(CO)12, which were synthesized in situ after a cation exchange process under CO in the large pores of zeolites such as HY, NaY, or 13X.25,26 The zeolite-entrapped carbonyl clusters are stable towards oxidation-reduction cycles this is in sharp contrast to the behavior of the same clusters supported on non-porous inorganic oxides. At high temperatures these metal carbonyl clusters aggregate to small metal particles, whose size is restricted by the dimensions of the zeolitic framework. Moreover, for a number of reactions, the size of the pores controls the size of the products formed thus a higher selectivity to the lower hydrocarbons has been reported for the Fischer Tropsch reaction. 

These observations illustrate that there are two transformations open to metallocarboxylic acid intermediates reversible loss of OH" accompanied by oxygen exchange, and metal-hydride formation with expulsion of C02. Our entry into this area of chemistry was in 1975 when extensive studies of oxygen lability in metal carbonyl cations were initiated (10). These... 

We have exploited this base catalysis of the oxygen exchange process to effect oxygen lability in the less electrophilic carbonyl sites of neutral metal carbonyl species. Because [MCOOH] intermediates are readily decarboxylated in the presence of excess hydroxide ion, in order to observe oxygen exchange processes in neutral metal carbonyl complexes it was convenient to carry out these reactions in a biphasic system employing phase transfer catalysis () (16, 17. 18). Under conditions (eq. 7) the... 

CO is an excellent probe molecule for probing the electronic environment of metals atoms either supported or exchanged in zeolites. Hadjiivanov and Vayssilov have published an extensive review of the characteristics and use of CO as a probe molecule for infrared spectroscopy [80]. The oxidation and coordination state of the metal atoms can be determined by the spectral features, stability and other characteristics of the metal-carbonyls that are formed. Depending on the electronic environment of the metal atoms, the vibrational frequency of the C-O bond can shift. When a CO molecule reacts with a metal atom, the metal can back-donate electron density into the anti-bonding pi-orbital. This weakens the C-O bond which results in a shift to lower vibrational frequencies (bathochromic) compared to the unperturbed gas phase CO value (2143 cm ) [62]. These carbonyls form and are stable at room temperature and low CO partial pressures, so low temperature capabilities are not necessary to make these measurements. 

Large-pore zeolites modified with metal ions (by ion exchange), metallocenes (e.g., [Cp2Ni], [Cp2Ru], [Cp2pe] and [CpMn(CO)3]) or metal carbonyls (e.g., [Ni(CO)4],... 

Dimethylformamide metal carbonyl derivatives, 8 27 solution, divalent lanthides, solution exchange, 42 61-63 Dimethylgallane, 41 192-194 Dimethylgallium tetrahydroborate, 41 188-189 Dimethylglyoxime... 

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