Carbonyl --complexes, preparation

Polymetallic iridium carbonyl complexes, preparation, 7, 291 Polymetallic nickel—alkenes, synthesis and reactivity, 8, 139 Polymetallocenes... 

Selected Transition Metal Carbonyl Complexes Prepared by Microwave Heating... 

Representative icosahedral metaUacarborane carbonyl complexes are prepared as shown (193). 

Conjugated dienes sucb as butadiene and its open-chain analogues can act as 17 ligands the complexes are u.sunlly prepared from melal carbonyl complexes by direct replacement of 2CO by the diene. Isomerization or rearrangement of the diene may occur a.s indicated schematically below ... 

Carboxylic acids, a-bromination of 55, 31 CARBOXYLIC ACID CHLORIDES, ketones from, 55, 122 CARBYLAMINE REACTION, 55, 96 Ceric ammonium nitrate [Ammonium hexa mtrocerate(IV)[, 55, 43 Chlorine, 55, 33, 35, 63 CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55, 84 Cinnamomtnle, a-phenyl- [2-Propeneni-tnle 2,3-diphenyl-], 55, 92 Copper(l) iodide, 55, 105, 123, 124 Copper thiophenoxide [Benzenethiol, copper(I) salt], 55, 123 CYCLIZATION, free radical, 55, 57 CYCLOBUTADIENE, 55, 43 Cyclobutadieneiron tricarbonyl [Iron, tn-carbonyl(r)4-l,3-cyclo-butadiene)-], 55,43... 

Carbonyl Nitric Oxides. Another group of metal-carbonyl complexes, worthy of investigation as CVD precursors, consists of the carbonyl nitric oxides. In these complexes, one (or more) CO group is replaced by NO. An example is cobalt nitrosyl tricarbonyl, CoNO(CO)3, which is a preferred precursor for the CVD of cobalt. It is a liquid with a boiling point of 78.6°C which decomposes at 66°C. It is prepared by passing NO through an aqueous solution of cobalt nitrate and potassium cyanide and potassium hydroxide. ... 

Uson, R., Laguna, A., Abad, J.A. and Dejesus, E. (1983) Preparation Of Monomeric Neutral Or Anionic Tris (Polyfluorophenyl)-Thalbum(III) And Of Anionic Heteronuclear Tris (Polyfluorophenyl)-Thallium Metal-Carbonyl-Complexes. Journal of the Chemical Society, Dalton Transactions, (6), 1127-1130. 

In the early work on the thermolysis of metal complexes for the synthesis of metal nanoparticles, the precursor carbonyl complex of transition metals, e.g., Co2(CO)8, in organic solvent functions as a metal source of nanoparticles and thermally decomposes in the presence of various polymers to afford polymer-protected metal nanoparticles under relatively mild conditions [1-3]. Particle sizes depend on the kind of polymers, ranging from 5 to >100 nm. The particle size distribution sometimes became wide. Other cobalt, iron [4], nickel [5], rhodium, iridium, rutheniuim, osmium, palladium, and platinum nanoparticles stabilized by polymers have been prepared by similar thermolysis procedures. Besides carbonyl complexes, palladium acetate, palladium acetylacetonate, and platinum acetylac-etonate were also used as a precursor complex in organic solvents like methyl-wo-butylketone [6-9]. These results proposed facile preparative method of metal nanoparticles. However, it may be considered that the size-regulated preparation of metal nanoparticles by thermolysis procedure should be conducted under the limited condition. 

The first homoleptic, dinuclear platinum(I) carbonyl complex [Pt2(CO)6]2+ has been prepared by dissolving Pt02 in concentrated sulfuric acid under a CO atmosphere.92,93 The structure is rigid on the NMR time scale at room temperature. DFT studies suggested a staggered structure for the dimer.92,93... 

The first carbonyl complex of gold, [AuCl(CO)], was prepared in 192 52080,2081 and since then only a few more derivatives have been obtained. The [AuBr(CO)] derivative was prepared later and is unstable in the solid state.2082,2083 The reductive carbonylation of Au(S03F)3 in fluorosulfonic acid leads via [Au(CO)2]+ (solvent) to solid [Au(S03F)(C0)] (Scheme 30).2084 [Au(CO)2]+ salts are produced in strongly ionizing protic acids or in Lewis acids such as SbF5. 

Most of the substitution reactions with the homoleptic Tc(I) isocyanide complexes presented in the preceding section had to be performed at elevated temperatures and were often characterized by low yield. The reason for this behaviour is the exceptionally high kinetic and thermodynamic stability of this class of compounds. From this point of view, 4a are not very convenient or flexible starting materials, although they are prepared directly from 3a in quantitative yield. The exceptionally high kinetic and thermodynamic stability is mirrored by the fact that it was not possible to substitute more than two isocyanides under any conditions. On the other hand, oxidation to seven-coordinated Tc(III) complexes occurs very readily. Technetium compounds of this type, which are not expected to be very inert, could open up a wide variety of new compounds, but this particular field has not been investigated very thoroughly. A more convenient pathway to mixed isocyanide complexes that starts with carbonyl complexes of technetium will be described in Sects. 2.3 and 3.2. 

MetalIa-/3-diketonate complexes, such as 1, are conveniently prepared by reacting acylmetal carbonyl complexes with strong bases that can also react as nucleophiles, such as organolithium, Grignard, or boron hydride reagents [Eq. (1)]. These reactions can be followed by IR spectroscopy. 

Bis(i7-cyclopentadienyl)dicarbonylzirconium (2) was the first fully characterized zirconium carbonyl complex to appear in the scientific literature. In 1976 this complex was reported simultaneously and independently by American (6), French (7), and Italian (8) research groups. Previous to this, many of the methods which proved successful for the preparation of Cp2Ti(CO)2 (1) failed for the formation of Cp2Zr(CO)2 (2) (5,26,38). 

Like zirconium, the first fully characterized carbonyl complex of hafnium was reported in 1976 by Thomas and Brown (6). This complex, bis(i7-cyclopentadienyl)dicarbonylhafnium (3) was prepared via the reductive carbonylation of Cp2HfCl2 using sodium amalgam. While the reaction proceeded to give a moderate yield of 3 (30%), this corresponded to only 60 mg of isolated product. 

Two other functionally substituted 17-cyclopentadienyl titanium dicarbonyl complexes prepared by Rausch and co-workers include the vinyl Cp compound (i7-C5H4CH=CH2)CpTi(CO)2 (81) and the carbomethoxy Cp compound (rj-C5H4C02Me)CpTi(C0)2 (82). Both were synthesized via the aluminum-induced reductive carbonylation of the corresponding dichloride derivatives. 

The only Zr(0) carbonyl complex has been prepared by Wreford and co-workers. When ZrCl4 was treated with l,2-bis(dimethyl-phosphino)ethane (dmpe), and then subsequently reduced with sodium amalgam in the presence of 1,3-butadiene, the dmpe bridged dimer, [(t/-C4H6)2Zr(dmpe)]2(dmpe) (65), resulted (114). The brown crystalline dimer 65 was found to be in equilibrium with the 16-e- coordinatively unsaturated complex, (tj-C4H6)2Zr(dmpe) (66), and free dmpe. When toluene solutions of 65 were exposed to CO at —45°C, 1 equivalent of CO per equivalent of Zr was consumed and the CO adduct (r/-C4H6)2Zr-(dmpe)(CO) (67) precipitated as a yellow solid. If these mixtures were allowed to warm above -22°C under vacuum, the precipitate dissolved and the consumed CO evolved (114). Complex 67 could be isolated by... 

The only description of (rj-arene)carbonyl complexes of Ti, Zr, and Hf has again been in the patent literature. Ethyl Corporation reported the preparation of (T/-C6H6)Ti(CO)3 via the carbonylation of TiPh2Cl2 (116). 

Formally, in each of these cases the disproportionation produces a positive metal ion and a metal ion in a negative oxidation state. The carbonyl ligands will be bound to the softer metal species, the anion the nitrogen donor ligands (hard Lewis bases) will be bound to the harder metal species, the cation. These disproportionation reactions are quite useful in the preparation of a variety of carbonylate complexes. For example, the [Ni2(CO)6]2 ion can be prepared by the reaction... 

Fischer-Tropsch synthesis could be "tailored by the use of iron, cobalt and ruthenium carbonyl complexes deposited on faujasite Y-type zeolite as starting materials for the preparation of catalysts. Short chain hydrocarbons, i.e. in the C-j-Cq range are obtained. It appears that the formation and the stabilization of small metallic aggregates into the zeolite supercage are the prerequisite to induce a chain length limitation in the hydrocondensation of carbon monoxide. However, the control of this selectivity through either a definite particle size of the metal or a shape selectivity of the zeolite is still a matter of speculation. Further work is needed to solve this dilemna. 

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