Copper carbonyls

The gases used were purchased premixed in aluminum cylinders to avoid carbonyl formation. The high purity gas mixture was further purified by a zeolite water trap and a copper carbonyl trap. The gas pressure in the reactor was measured with a capci-tance manometer and the fTow monitored with a mass fTow controT-ler. The typical gas flow rates were 15 cc/min (STP) and the maximum conversion was 1% based on integration of hydrocarbon products. The hydrocarbon products were analyzed by gas chromatography (temperature programmed chromosorb 102, FID). 

Although some copper carbonyls were known before, the first crystallographic characterization of one of these compounds was carried out in 1973 with TpCu(CO). Similar complexes have been reported to date, particularly in the last decade, since the GO ligand can be used as a probe to estimate electronic and also, to some extent, steric effects of the Tpx ligand. The related trispyrazolylmethane group has also been employed to yield the... 

Figure 38 X-ray structures of the copper carbonyls 95 and 96. 95 reproduced with permission from ACS publications.

CsICl2 Cesium iododichloride, 4 9 CsNOs Cesium nitrate, 4 6 1-hydrogen nitrate, 4 7 CsN3 Cesium azide, 1 79 CuBr Copper(I) bromide, 2 3 CuCl Copper(I) chloride, 2 1 [CuC1-CO]-2H20 Copper carbonyl chloride, 2 4... 

Copper carbonyl ferrocyanide, Cu3[Fe(CN)5.CO]2, is obtained1 by double decomposition in aqueous solution of copper sulphate and potassium carbonyl ferrocyanide. It forms as a yellowish green gelatinous precipitate, which is insoluble in dilute nitric or sulphuric acid, and which becomes an anhydrous dark brown powder at 110° C. 

BCuN6OCioH10, Copper , car-bonyl[hydrotris(pyrazolato)borato]-, 21 108 BCuN6OCi6H22, Copper , carbonyl[tris(3,5-dimethylpyrazolato)hydroborato]-, 21 109 BCuNsOCisHn, Copper , car-bonyl[tetrakis(pyrazolato)borato]-, 21 110 BNNaC2H3, Borate 1 -), cyanotri[(2//)hydro)-, sodium, 21 167... 

Carbon monoxide is absorbed by solutions of chlorocuprates(l), and the halogen bridged dimer (CuClCO)2 can be obtained as crystals. The gas is absorbed quantitatively by aqueous ammonia solutions of Cu1 and can be regenerated by acidification. Other unstable copper carbonyls such as /75-C5H5Cu(CO), [Cuen(CO)]Cl and CuCl(CO)(Me2N=CH2)+ can be isolated.20 A binary carbonyl formed when copper atoms produced thermally are trapped in a CO matrix at 20 °K can be detected by its infrared spectrum.201... 

Figure 11. Structure of mixed-metal ruthenium-copper carbonyl ic...

Immediately after application of synthesis gas pressure, a band (1) is observed for dissolved CO at 2130 cm . The peak at 2060 cm indicates a mononuclear copper carbonyl complex. The complex of type [Cu(CO)L] (L = ligand), formed in situ, is the active catalyst. After a reaction time of 140 min, an aldehyde band appears at 1720 cm (3), while the sharp olefin peak at 1640 cm (4) continually decreases in intensity. The catalyst is only effective in the temperature range 160-180 °C and rapidly decomposes above 180 °C. 

The branched products predominate in the reaction product. The reaction is a modified Reppe-Koch conversion. The copper carbonyl ion functions as a CO suppher, transporting the CO from the gas phase to the H2SO4 solution (Scheme 1.4). 

Yoneda, N., Fukuhara, T. Carboxylation reaction of diisobutene and 1-octene with carbon monoxide using a copper carbonyl BF3-H2O catalyst system. Chem. Lett. 3, 607 (1974)... 

The Tp ligands have been successfirUy used to prepare the stable copper carbonyl complexes as [Cu(Tp)(CO)]. Recently a solution of CuTp has been employed to improve the solubihty of CO that upon release from the complex has been used in low-pressure, one-pot palladium-mediated carbonylation reactions for the production of C-radiolabeled amides and ureas. The coordination chemistry oftris(3-R-5-R -pyrazolyl)borate ligands bearing different substituents (Tp , Tp ", "ppPhos.Me ... 

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