Infrared spectra metals

Otsuka et al. (107) describe [Ni(CNBu )2], as a reddish brown microcrystalline substance, which is extremely air-sensitive. It can be recrystallized from ether at —78°C, and is soluble in benzene in the latter solution the infrared spectrum (2020s, br, 1603m, 1210m) and proton NMR (three peaks of equal intensity at t8.17, 8.81, and 8.94) were obtained. Neither analytical data nor molecular weight is available on this complex. The metal-ligand stoichiometry is presumably established by virtue of the molar ratio of reactants and by the stoichiometries of various reaction products. 

The mixed-metal tetranuclear derivatives that have been prepared are H2Re2Ru2(CO)i6, CReRu3(CO)16] , HMnOs3(CO)16, and HReOs3(CO)18 (238). All the complexes result from the reaction of the carbonyl, M3(CO)i2, with the related anion, [Mn(CO)5]- or [Re(CO)s]. The ruthenium anion [ReRu3(CO)16] was isolated as its tetramethylammo-nium salt. The infrared spectrum was complex, but consistent with... 

Pentacarbonyl(diphenylmethylene)tungsten(0) is a moderately air-stable soild that is readily soluble in most organic solvents. The resulting solutions are air and light sensitive and decomposed thermally at about 50°. The infrared spectrum of a heptane solution shows bands in the metal carbonyl region at 2070 (m), 1971 (s), and 1963 (s) cm"1, characteristic of a group VI pentacar-bonyl species. The proton NMR spectrum in CS2 or acetone-d6 shows a complex multiplet at 5 7.2 relative to internal tetramethylsilane. 

The intermediate cyclooctene complex appears to be more reactive with respect to CS coordination and more sensitive to oxidation when the arene ring bears electron-withdrawing groups (e.g., C02CH3). Dicarbonyl(methyl rj6-benzoate)-thiocarbonyl)chromium is air stable in the solid state and reasonably stable in solution.9 The infrared spectrum exhibits metal carbonyl absorptions at 1980 and 1935 cm"1 and a metal thiocarbonyl stretch at 1215 cm"1 (Nujol) (these occur at 1978, 1932, and 1912 cm"1 in CH2C12 solution).10 Irradiation of the compound in the presence of phosphite or phosphine leads to slow substitution of CO by these ligands, whereas the CS ligand remains inert to substitution. The crystal structure has been published."... 

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