Metal Carbonyls

The following article is from The Great Soviet Encyclopedia (1979). It might be outdated or ideologically biased.

Metal Carbonyls


compounds of metals with carbon monoxide, with the general formula Mem (COn). Nickel car-bonyl, Ni(CO)4, was the first to be discovered (1890), and since then the carbonyls of several metals and nonmetals have been prepared. Metal carbonyls may be either “mononuclear” or “polynuclear,” depending on the number of metal atoms in the molecule; compound metal carbonyls, such as [Co(CO)4]2Zn, also exist.

The carbonyls of nickel, iron, osmium, and ruthenium are liquids; most other carbonyls are crystalline. Metal carbonyls are diamagnetic, highly volatile, and extremely toxic. Only halide carbonyls, Me(CO)X, which are stable only in a carbon monoxide atmosphere, exist for copper, silver, and gold. Metal carbonyls decompose when heated above a certain temperature, releasing carbon monoxide and metal in a finely dispersed state. The physical properties of the principal metal carbonyls are presented in Table 1 (the carbonyls shown are readily soluble in organic solvents).

Table 1. Physical properties of some metal carbonyls
 Boiling point (°C)Melting point (°C)Density at 20°C (g/cm3)Solubility in water

A common method of preparing metal carbonyls involves the reaction of carbon monoxide with metals or their salts at high temperatures and pressures. The metal carbonyls that are of the greatest commercial significance are nickel carbonyl, Ni(CO)4; cobalt carbonyl, Co(CO)4; and iron carbonyl, Fe(CO)5. Carbonyls are used for the preparation of pure metals, which form upon their thermal dissociation. Thermal dissociation of cobalt, nickel, and chromium carbonyls is used in the application of metallic coatings, particularly on surfaces of complex shape. Cobalt and nickel carbonyls are catalysts in important chemical processes—for example, in the synthesis of carboxylic acids and their derivatives from olefins, and in the synthesis of acrylic acid from acetylene during hydroformylation:

Metal carbonyls are good antiknock compounds for motor fuels; however, the formation of oxides that are difficult to remove takes place during combustion. Certain carbonyls serve in the preparation of absolutely pure carbon monoxide.


Belozerskii, N. A. Karbonily metallov. Moscow, 1958.
Khimiia koordinatsionnykh soedinenii. Edited by J. Bailar and D. Busch. Moscow, 1960. (Translated from English.)
Khimiia metalloorganicheskikh soedinenii. Edited by H. Zeiss. Moscow, 1964. Pages 538–604. (Translated from English.)


The Great Soviet Encyclopedia, 3rd Edition (1970-1979). © 2010 The Gale Group, Inc. All rights reserved.
References in periodicals archive ?
Therefore, a group of transition metal carbonyls or boranocarbonates, known as CO-releasing molecules (CORMs), which can release CO upon transformation becomes the best alternative to gas administration [2-5, 9,10].
Vieira, "Metal carbonyl prodrugs: CO delivery and beyond," in Bioorganometallic Chemistry: Applications in Drug Discovery, Biocatalysis, and Imaging, pp.
Chapters are: environmental applications of multifunctional nanocomposite catalytic materials; chemical transformation of molecular precursor into well-defined nanostructural functional framework via soft chemical approach; graphenes in heterogeneous catalysis; gold nanoparticlesugraphene composites material; hydrogen generation from chemical hydrides; ring-opening polymerization of lactide; catalytic performance of metal alkoxides; cycloaddition of Co20 and epoxides over reusable solid catalysts; catalytic metal-/bio-composites for fine chemicals derived from biomass production; homoleptic metal carbonyls in organic transformation; zeolites; optimizing zeolitic catalysis for environmental remediation.
Typical compounds include metal alkyls, metal alkoxides, metal diketonates, metal amidinates, and metal carbonyls. Each of these types of compounds displays different reactivity in the CVD/ALD reaction chamber, leading to the formation of different types of films.
Covering first metal complexes then transition metal chemistry, they discuss such topics as the correct empirical formula of complexes, isomerism and stereochemistry, metal carbonyls and nitrosyls, the vanadium group, and the actinides.
Photochemical reactions of group 6 metal carbonyls with N-salicylidene-2-hydroxyaniline and bis-(salicylaldehyde)phenylenediimine, J.
These values are in close resemblance to the values of v (CO) vibration for other nitrogen containing disubstituted group-6 metal carbonyls [13, 16, 18, 19].
R&D at Leeds has seen the application of supercritical fluid carbon dioxide (SC-[CO.sub.2]) for the fractionation of polymers, dyeing of textiles and paper, production of fine particles by dissolving and precipitating metal carbonyls, and isolation of naturally occurring pesticides from plant matter.
The first seven chapters discuss medicinal chemistry, covering the topics of organometallic enzyme inhibitors, organometallic steroid analogs, chirality in chemotherapeutics, gold complexes, the antimalarial ferroquine, metal carbonyls as prodrugs, and the electronics of nitrosyl and thiol iron complexes.
The complexes, 1-9 were prepared by the photochemical reactions of metal carbonyls M[(CO).sub.6] (M = Cr, Mo, W) with [SB.sup.1], [SB.sup.2], [SB.sup.3] and were obtained in 65 -75% yields by the method given below.
Metal carbonyl complexes have found wide use in industrial applications as catalysts after the first binary complex, Ni[(CO).sub.4], was synthesized by Mond in 1890, although the first metal carbonyl complex, [[Pt(CO)[Cl.sub.2]].sub.2] was synthesized in 1868 [1].