Carbon monoxide cobalt clusters

The chemical reactivity of cobalt cluster anions, Co (n = 2-8), toward 02, N2, and CO have been investigated using a flow tube reactor (226). The reactivity was found to be in the order 02 > CO > N2 the least reactive ligand N2 only reacted with C07 and Cog. The primary reaction of oxygen was the removal of one or two cobalt atoms from the cluster. Carbon monoxide reacts by multiple additions giving saturation limits shown in Table V. 

The methods described here are based on the thermal stability of such clusters under CO pressure.4 In the case of Co2Fe(CO)9S, the complex itself is stable under hydroformylation conditions (130-180 °C, 50-150 bar CO and H2) and is formed under such conditions from almost every sulfur-containing substance, iron, cobalt, and carbon monoxide.1 Ethanethiol is used in the procedure as the sulfur source because of its reactivity. The dihydride cluster Fe3H2(CO)9S is not directly accessible by this method because it is a thermally much less stable species but the anion Fe3H(CO)9S" can be prepared in this way and its acidification yields the desired complex. 

The data in Table XIV suggest that the positive charge in complexes Via, b, and c has been delocalized to a large extent into the cluster substituent. The observed slight increase in shielding of the carbon atoms of the carbon monoxide ligands when the alcohols are converted to the carbonium ions speak in favor of this view. If the cobalt atoms are more... 

Finally, cobalt carbide-carbonyl clusters have recently been isolated through a two-step synthesis. First of all, the well-known Co3(CO)9CCl is prepared from Co2(CO)8 and CCh, and then the hexanuclear carbide dianion [Co6(CO)i5C]2- is obtained in good yields (9) by further reaction with Xa[(, o(CO)4] in diisopropylether [see Eqs. (18) and (19)]. Further redox condensation between [Oo6(CO)i5C]2-and Co4(CO)i2 [see Eq. (11)] gives the square antiprismatic octanuclear cluster [Cdo8(Cdt )i8 C]2- (13). Both these carbide derivatives, as well as all of the other cobalt high nuclearity clusters, are sensitive to air and react with carbon monoxide at atmospheric pressure. 

CF3H, Methane, trifluoro-cadmium complex, 24 55 mercury complex, 24 52 CF3NOS, Imidosulfurous difluoride, (fluorocarbonyl)-, 24 10 CH2, Methylene ruthenium complex, 25 182 CH2CI4P2, Phosphine, methylenebis-(dichloro)-, 25 121 CH3, Methyl cobalt complexes, 23 170 mercury complexes, 24 143-145 platinum complex, 25 104, lOS CNO, Cyanato silicon complex, 24 99 CN2OS2, l,3k, 2,4-Dithiadiazol-5-one, 25 53 CO, Carbon monoxide chromium complexes, 21 1, 2 23 87 cobalt complex, 25 177 cobalt, iron, osmium, and ruthenium complexes, 21 58-65 cobalt-osmium complexes 25 195-197 cobalt-ruthenium cluster complexes, 25 164... 

OC, Carbon monoxide chromium complex, 21 1, 2 chromium and tungsten complexes, 23 27 cobalt complex, 25 177 cobalt complexes, 23 15-17, 23-25 cobalt, iron, osmium, and ruthenium complexes, 21 58-65 cobalt-osmium complexes, 25 195-197 cobalt-ruthenium cluster complexes, 25 164... 

The selective production of methanol and of ethanol by carbon monoxide hydrogenation involving pyrolysed rhodium carbonyl clusters supported on basic or amphoteric oxides, respectively, has been discussed. The nature of the support clearly plays the major role in influencing the ratio of oxygenated products to hydrocarbon products, whereas the nuclearity and charge of the starting rhodium cluster compound are of minor importance. Ichikawa has now extended this work to a study of (CO 4- Hj) reactions in the presence of alkenes and to reactions over catalysts derived from platinum and iridium clusters. Rhodium, bimetallic Rh-Co, and cobalt carbonyl clusters supported on zinc oxide and other basic oxides are active catalysts for the hydro-formylation of ethene and propene at one atm and 90-180°C. Various rhodium carbonyl cluster precursors have been used catalytic activities at about 160vary in the order Rh4(CO)i2 > Rh6(CO)ig > [Rh7(CO)i6] >... 

The cobalt carbonyls are prepared by the disproportionation reaction of [Co2(CO)g] in the presence of Lewis bases or by the reduction of cluster cobalt carbonyls with the alkali metals. The iridium compounds are obtained during reduction of [Ir4(CO)i2] with sodium in ether solution. The rhodium carbonyls are usually synthesized by reduction of [Rh2Cl2(CO)4] or [RhClg] " with carbon monoxide in basic medium or by nucleophilic attack of bases on the carbonyl group of carbonyl clusters (see preparation of [M4(CO)i2] and [M6(CO)i6]). 

The gallium and indium atoms maintain their typical tricoordination and do not interact with carbon monoxide which interacts only with the transition metal atoms (manganese). Such a behaviour means that non-transition and transition metal atoms maintain their own properties even when directly bound also in a complex cluster cage. In agreement with this point in a compound as Sn[Co(CO)4] 2 [Mn(CO)s] 2 [137] the cobalt and manganese atoms maintain their typical coordination as the tin atom. 

A trinuclear cobalt(I) complex, PhCCo3(CO)9, can also catalyse the reduction of nitro compounds in the presence of hydroxide ion at room temperature under a normal pressure of CO [49]. Satisfactory results were obtained under phase transfer conditions. The catalyst and the aromatic nitro compounds were dissolved in benzene under carbon monoxide and an aqueous solution of sodium hydroxide containing cethyltrimethylammonium bromide was added. At a substrate/cat =10 ratio, ca. 60-80 % of amine was obtained in a 18 h reaction. The reaction also proceeded in a homogeneous phase (methanol-water, methanol, dioxane-water) but with lower conversions (less than 45 %). Cobalt complexes such as MeCCo3(CO)9 and MeCo(CO)4 were also active, but less effective. At the end of the reaction, the catalyst was recovered only in part (ca. 15 %). In the organic phase, an IR absorption at 1891 cm, attributable to [Co(CO)4] anion, was observed. Strangely enough, the preformed [Co(CO)4] anion has not been tested as catalyst. The active species was supposed to be the hydride cluster anion reported in Scheme 6. 

Bimetallic phase-transfer-catalysis is a process whereby a reaction that occurs using two different metal complexes, does not proceed in the absence of either metal species, or proceeds only at reduced rate. An apparent system of this class has been reported, in which Co2(CO)g and [RhCl(l,5-hexadiene)]2 mutually increased their reactivity when used as catalysts for the conversion of nitrobenzene to aniline in a biphasic system (benzene, aqueous NaOH, dodecyltrimethylammonium chloride) in a carbon monoxide atmosphere [73]. However, another member of the same research group later showed [74] that the apparent bimetallic promotion was due to the fact that the alkylammonium salt used as a phase-transfer agent actually inhibited the activity of the active rhodium complex (apparently a cluster, which is active in the absence of both the alkylammonium salt and the cobalt compound) by rendering it insoluble. The added Co2(CO)g reacts with the alkylammonium salt to generate... 

Chen AA, Kaminsky M, Geoffrey GL, Vannice MA. Carbon monoxide hydrogenation over carbon-supported iron-cobalt and potassium-ironicobalt carbonyl cluster-derived catalysts. 

In the case of carbonyl metal clusters, the presence of free carbon monoxide notoriously affects the reduction processes inducing condensations as well as degradation of the clusters species. Thus the reduction of the tetranuclear cobalt cluster 04(00)4 with lithium, sodium, or potassium in which the final product is the hexanuclear cluster [Co6(CO)i5] is an illustrative example of the complexity of such reactions. 

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