Nickel steric structures

Nickel (continued) polysulfide complex, 31 98 half chair conformation, 31 115 porphyrin complexes, 32 13 in proteins, 47 284-285 quadruply bridged dimers, 40 211-214 steric structures, 40 190-194 quaternary phosphonium salts of, 6 31-32 redox chemistry probes of structure, 32 243-245 steric and electronic requirements, 32 242-243... 

Another new catalyst generation based on iron and cobalt. The direct iron analogs of the nickel-diimine catalysts derived from structures (25) and (26) did not seem to be very active in olefin polymerization at all. The electronic and steric structure analysis shows why the nickel d -system favors a square planar coordination sphere but the iron d -system favors a tetrahedral one. It is very likely that these tetrahedral coordination sites are not available for olefin insertion, and hence no polymerization can take place. 

Although the actual reaction mechanism of hydrosilation is not very clear, it is very well established that the important variables include the catalyst type and concentration, structure of the olefinic compound, reaction temperature and the solvent. used 1,4, J). Chloroplatinic acid (H2PtCl6 6 H20) is the most frequently used catalyst, usually in the form of a solution in isopropyl alcohol mixed with a polar solvent, such as diglyme or tetrahydrofuran S2). Other catalysts include rhodium, palladium, ruthenium, nickel and cobalt complexes as well as various organic peroxides, UV and y radiation. The efficiency of the catalyst used usually depends on many factors, including ligands on the platinum, the type and nature of the silane (or siloxane) and the olefinic compound used. For example in the chloroplatinic acid catalyzed hydrosilation of olefinic compounds, the reactivity is often observed to be proportional to the electron density on the alkene. Steric hindrance usually decreases the rate of... 

Quite a number of silylnickel and silylenenickel compounds have been reported, and only a few can be cited here2305-2309 Bis(silyl)nickel complexes have been implicated as important intermediates in Ni-catalyzed double silylation of various organic substrates. Using an o-bis(dimethylsilyl)carborane ligand, complex (930) could be isolated and structurally characterized 2310 Its unusual thermal stability is attributed to the advantageous steric and electronic properties of the carboranyl unit. (930) undergoes... 

These structures can, for steric reasons, be formed only when the coordination number of the nickel atom is 7 or less. We call this species the subcarbonyl species as it is an intermediate in the formation of Ni(CO)4-Further evidence on this point will be given below. 

Relevant bond distances and angles of dinitrogen complexes whose X-ray structure has been determined are shown in Table 15. The complex [ Ni(PCy3)2 2N2] (Figure 1) is dimeric, with the N2 molecule coordinated end-on to the two nickel atoms. Each nickel atom is surrounded by four cyclohexyl groups of the phosphine ligands which give some steric protection.227 IR, 31P and HNMR spectra indicate that in toluene solutions of this complex the equilibrium shown in equation (60) operates.236... 

The important point to appreciate is that the formal valency of zinc is satisfied by two bonds to sulfur so that the additional interactions are indeed hypervalent interactions. Thus, the nature of the adopted structures arises from the ability of the central element to form hypervalent, or secondary, interactions and it is proposed that this ability is moderated by steric considerations associated with the alkyl substituents. As noted from the structural studies for the uncoordinated xanthate anions summarized earlier in Section II, there are no electronic differences among the xanthate ligands that can be correlated with the nature of the oxygen-bound substituent. This conclusion is vindicated by the homogeneity of the molecular structures of the binary nickel xanthates as... 

Zinc and other metal ions have been found to promote pyrrole hydrogen ionization in 2-(2 -pyridyl)imidazole.269 Complexation studies114 on the systems N-methyl-histamine and NN-dimethylhistamine with bivalent zinc, copper, cobalt, and nickel have shown that the stabilities of the complexes follow the Irving-Williams series. With respect to the variation of a ligand with the same metal ion, the stability decreases in the series histamine, N-methylhistamine, NN-dimethylhistamine, possibly as a result of steric hindrance. The complexes are assigned the structure (12). 

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