Ni system

Table 16 Structural and magnetic parameters for ID traw5-[Ni(/i-l,3-N3)Ni] systems angles Ni—N—N and...

It is particularly helpful that we can take the Cu-Ni system as an example of the use of successive deposition for preparing alloy films where a miscibility gap exists, and one component can diffuse readily, because this alloy system is also historically important in discussing catalysis by metals. The rate of migration of the copper atoms is much higher than that of the nickel atoms (there is a pronounced Kirkendall effect) and, with polycrystalline specimens, surface diffusion of copper over the nickel crystallites requires a lower activation energy than diffusion into the bulk of the crystallites. Hence, the following model was proposed for the location of the phases in Cu-Ni films (S3), prepared by annealing successively deposited layers at 200°C in vacuum, which was consistent with the experimental data on the work function. 

Further progress in the study of the Cu-Ni system awaited the preparation and careful characterization of alloy films of known bulk and surface composition. The essential step was taken by Sachtler and his co-workers 28, 88, 114) who prepared Cu-Ni alloy films by successive evaporation of the component metals in UHV. After evaporation the films were homogenized by heating in vacuum at 200°C. The bulk composition of the alloys was derived from X-ray diffraction, and the photoelectric work function of the films was also measured. A thermodynamic analysis, summarized by Fig. 13, indicated that alloy films sintered at 200°C should consist, at equilibrium, of two phases, viz., phase I containing 80% Cu and phase II containing 2% Cu. Evidence was presented that alloys within the... 

Fig. 18. Phase diagram for the Cu-Ni system calculated from two available sets of thermodynamic data (70).

The Pt-Au system (162) is analogous to the Cu-Ni system in that it exhibits a wide miscibility gap (below 1258°C), and one metal (gold)... 

The isomer distribution of the nickel catalyst system in general is similar qualitatively to that of the Rh catalyst system described earlier. However, quantitatively it is quite different. In the Rh system the 1,2-adduct, i.e., 3-methyl-1,4-hexadiene is about 1-3% of the total C6 products formed, while in the Ni system it varies from 6 to 17% depending on the phosphine used. There is a distinct trend that the amount of this isomer increases with increasing donor property of the phosphine ligands (see Table X). The quantity of 3-methyl-1,4-pentadiene produced is not affected by butadiene conversion. On the other hand the formation of 2,4-hexadienes which consists of three geometric isomers—trans-trans, trans-cis, and cis-cis—is controlled by butadiene conversion. However, the double-bond isomerization reaction of 1,4-hexadiene to 2,4-hexadiene by the nickel catalyst is significantly slower than that by the Rh catalyst. Thus at the same level of butadiene conversion, the nickel catalyst produces significantly less 2,4-hexadiene (see Fig. 2). 

The Co system is more reactive as well as much more selective than the Ni and Rh catalyst systems (Table XVII). The best systems allow almost 100% conversion with almost 100% yield of c -l,4-hexadiene. The best of the Ni and Rh systems known so far are still far from such amazing selectivity. The tremendous difference between the Ni system and the Co or Fe system must be linked to the difference in the nature of the coordination structures of the complexes, i.e., hexacoordinated (octahedral complexes) in the case of Co and Fe and tetra- or penta-coordinated (square planar or square pyramidal) complexes in the case of Ni. The larger number of coordination sites allows the Co and Fe complex to utilize chelating phosphines which are more effective than monodentate phosphines for controlling the selectivity discussed here. These same ligands are poison for the Ni (and Rh) catalyst system, as shown earlier. 

This stereochemical model explains the stereochemistry of the hydrogenation of MAA over TA-Ni system. It also predicts that the TA-Ni catalyst can be effective for the enantioselective hydrogenation of some prochiral ketones with excellent e.e. values (70%). 

As mentioned above, the TA-Ni system can catalyze the hydrogenation of not only MAA but also of 2-alkanones. However, hydrogenation of 2-alkanones following the optimum conditions for MAA hydrogenation led to poor results. But the addition of small amount of acetic acid to the reaction mixture, as an additive, turned out to be essential for the enantioselective hydrogenation of these substrates. Further experiments indicated that acetic acid is not the only organic acid leading to such e.e. and the best results were obtained with pivalic acid (PA) in a concentration more than twice that of the substrate [214],... 

Owing to their numerous actual and potential applications, several ternary and complex systems of these metals, especially of aluminium, have been investigated a few examples of the systematics of Al-Me-X alloys are presented in 5.18 and in Fig. 5.41. Recent contributions to this subject have been given with the study of the systems R-Al-Cu (Riani et al. 2005, and references there in). These rare earth alloys, characterized by the formation of several intermediate phases, are interesting also as raw materials for the preparation of amorphous alloys. Regularities in the trends of their properties have been underlined. The experimental and calculated data relevant to the binary systems Al-Fe, Al-Ni and Fe-Ni have been examined and discussed in a paper concerning the assessment of the ternary Al-Fe-Ni system (Eleno et al. 2006). 

Electrocarboxylahon of benzylic chlorides has been intensively investigated in the presence of a Ni(II) complex as a catalyst [274-277]. Eenoprofen (165), an anti-inflammatory agent, is electrosyn-thesized from (164) in a THE/HMPA-Bu4NBE4-(C/Ni) system in the presence of NiCl2 (dppp) as a mediator under bubbling... 

The Barhier-type reaction of aldehydes and ketones with allyl halides (485) in the presence of Sml2, leading to homoallyl alcohols (486), has received recent interest as a one-step alternative to the Grignard reaction. However, the reactions require the use of stoichiometric amounts of the reducing Sm(III) species. Recently, the electroreductive Barhier-type allylation of carbonyl compounds in an SmH-mediated reaction has been developed [569]. The electrolysis of (485) is carried out in a DMF-SmCl3-(Mg/Ni) system in an undivided cell to give the adduct (486) in 50 85% yields (Scheme 168) [569]. Electrosynthesis of y-butyrolactones has been achieved by the reductive coupling of ethyl 3-chloropropionate with carbonyl compounds in the presence of a catalytic amount of SmCfi [570]. 

The Sm-assisted reductive dimerization of aromatic esters (487), leading to diketones (488) is carried out in a DMF-Bu4NBr-(Mg/Ni) system in the presence of SmCh as a mediatory catalyst (Scheme 169) [571]. 

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