Nickel compounds spectrum

The infrared spectrum (95,149a, 259) of nickelocene is extremely similar to that of ferrocene what differences there are confirm the view that the metal-ring bonding in the nickel compound is weaker, and the carbon-carbon bonding in the ring slightly stronger, than in ferrocene. 

When levuhnic acid (CH3CCH2CH2CO2H) was hydrogenated at high pressure over a nickel catalyst at 220°C a single product C5Hg02 was isolated in 94% yield This compound lacks hydroxyl absorption in its IR spectrum and does not immediately liberate carbon dioxide on being shaken with sodium bicarbonate What is a reasonable structure for the compound" ... 

Some data have been obtained on the activity of the catalyst in a reduced state [for nickel (141,143,144), palladium (144°), and molybdenum (145, 145a). In the case of nickel catalysts the formation of nickel in the zero oxidation state takes place during the reduction of the surface organometallic compound by H2. The infrared spectrum shows the total restoration of the concentration of Si—OH groups (139), so the reduction proceeds according to the scheme ... 

The first Ni Mossbauer spectrum of nickel in a bioinorganic compound with determinable EFG and isomer shift was reported for a nickel complex compound with planar [NiSJ core and considered as a model compound for hydrogenase. This Mossbauer spectrum from the formal Ni compound is presented in Fig. 7.16. The observed quadrupolar interaction can be understood in terms of ligand field theory. In this approach, the b g and levels (d y2 and d ) are not occupied which is expected to cause a large negative EFG contribution [32]. 

Fig. 7.16 Ni Mossbauer spectrum at 4.2 K of a nickel complex compound with planar [NiS4] core known as a model compound for hydrogenase (source Nio.gsCro.is (97% enriched) activated at Mainz Microtron) (from [32])...

The catalyst efficiency of these hydroalumination varies from a turnover number (TON) of 20-91. It is possible that the catalyst is deactivated by the presence of oxygen and water. Examination of the 31P NMR spectrum of the catalyst indicates that the phosphine monoxide and dioxide are formed in the presence of nickel prior to the addition of the substrate. Rigorous exclusion of oxygen and water is necessary in all these reactions. The enantioselective nickel-catalyzed hydroalumination route to dihydronaphthalenols may prove to be particularly important. Only one other method has been reported for the enantioselective syntheses of these compounds microbial oxidation of dihydronaphthalene by Pseudomonas putida UV4 generates the dihydronaphthalenol in 60% yield and >95% ee.1... 

XPS studies have been made on a number of compositions of these transition-metal oxides, and all indicate predominantly divalent nickel. Thus, for the 442 compound the Co spectrum is clearly Co +, and the Mn spectrum can be assigned to 80% Mn" + with 20% Mn +. The Ni spectrum is characterized by an intense and complicated satellite structure and consistent with 80% NP+ and 20 NP+. Studies on LiNio.33Mno.33Coo.3302, LiNio.5Mno.502, and... 

It has recently been shown that alkyl sulfoxides are good solvents for transition metal halides, and many adducts can be isolated 42, 84, 167, 227, 231). Nickel perchlorate takes up six dimethyl sulfoxide ligands, but the chloride apparently only three. It has been shown from the reflectance spectrum and from the high magnetic moment 42) that this compound should be formulated as [Ni(DMSO)6][NiCl4], in which the anion is tetrahedral. Infrared spectra 43, 127) show that the dimethyl sulfoxide coordination is through oxygen. Similar compounds are found with tetrahydro-thiophenoxide 84) ... 

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