Nickel redox with complexes

Nickel(III) peptide complexes have a tetragonally-distorted octahedral geometry as shown by electron spin resonance studies (19) and by reaction entropies for the Ni(III,II) redox couple (17). Axial substitutions for Ni(III)-peptide complexes are very fast with formation rate constants for imidazole greater... 

Dithio-oxamide (LH4) and dimethyldithio-oxamide (LMH2) form complexes of types Ni4(LH2)5 and Nig(LM)9 which have anomalous magnetic moments 405 The complex of iViV-diethylphenylazothioformamide (143) [NiL2]2+, formed by reaction of nickel perchlorate with the ligand in acetone, is a member of a facile redox series... 

The binuclear nickel-thiolate macrocyclic complex (101) displays noteworthy redox behavior, in which one-electron oxidation yields a Ni. Ni product with significant delocalization of the unpaired electron density onto the bridging thiolate ligands and not onto the second nickel ion. The charge delocalization consequently lies between the two redox extremes of nickel(III)-thiolate and nickel(II)-thiyl radical, thus mimicking the Ni-C state in [NiFeJhydrogenase (see 8ection 8). 

In methanol, Cl and 7tH+ ions exhibit a retarding effect. The stabilities of nickel(o)-phosphine complexes have been assessed these seem to depend more on the size of the phosphine and electronic effects on bond strengths are of secondary importance. In the oxidative addition of aryl halides to nickel(o)-phosphine complexes the reaction appears to proceed via an initial slow dissociation step to give Ni(PR3)2 which then attacks the organic species. The mechanism of oxidative elimination of these nickel species thus contrasts with that for the platinum(o)-phosphines where the dissociation of the ligand is rapid and the rate-determining step is that involving the redox interaction. The oxidation of tetrahedral cobalt(i) complexes with carbon tetrachloride has been described ... 

The Role of Redox Processes in Reactions Catalyzed by Nickel and Palladium Complexes with Anionic Pincer Ligands... 

Complexes o/M". The absence of any other oxidation state of comparable stability for nickel implies that compounds of Ni" are largely immune to normal redox reactions. Ni" forms salts with virtually every anion and has an extensive aqueous chemistry based on the green [Ni(H20)6] + ion which is always present in the absence of strongly complexing ligands. 

A novel polysiloxane, containing the isocyanide group pendent to the backbone, has been synthesized. It is observed to react with the metal vapors of chromium, iron and nickel to afford binary metal complexes of the type M(CN-[P])n, where n = 6, 5, 4 respectively, in which the polymer-attached isocyanide group provides the stabilization for the metal center. The product obtained from the reaction with Fe was found to be photosensitive yielding the Fe2(CN-[P])q species and extensive cross-linking of the polymer. The Cr and Ni products were able to be oxidized on exposure of thin films to the air, or electrochemically in the presence of an electron relay. The availability of different oxidation states for the metals in these new materials gives hope that novel redox-active polymers may be accessible. 

Also, the structure of the Ni11 complex (379) with the related ligand dimethyltetrathiomalonate has been determined.997 The geometry at the nickel center is approximately square planar with an inversion center. (379) shows reversible redox properties 998 Oxidation with I2 affords 1,3-bis (methylthio)-1,2-dithiolium triiodide. 

Mechanism 3 involves NiOH in at least three reactions, and Ni(OH)2 as the active Ni reactant in solution. Since increasing the concentration of the complex-ant(s) in solution will reduce the concentration of both unhydrolyzed and hydrolyzed metal ions, arguments of complexation cannot be readily employed to either support or discount this mechanism. However, it has been this author s experience in formulating electroless Co-P solutions with various complexants for Co2+ that improper complexation which results in even a faint precipitate of hydrolyzed cobalt ions yields an inactive electroless Co-P solution. Furthermore, anodic oxidation of hypo-phosphite at Ni anodes does not proceed at a significant rate under conditions where the surface is most probably covered with a passive film of nickel oxide [48], e.g. NiO.H20, which would be expected to oxidize the reducing agent via a cyclic redox mechanism. 

The anion [Fe3Co(CO)12] has recently been reported to be prepared by Chini from the redox reaction of Fe3(CO)12 with Co(CO)infrared spectra indicate a Co4(CO)i2 structure with nickel in the basal plane (234). 

The redox condensation shown in Eq. (9) gives rise to the dianion [Fe3Ni(CO)12]2 and it has also been possible to isolate salts of the corresponding hydride, [Fe3Ni(CO)12H]- (30.5 r). The presence of infrared absorptions due to bridging carbonyls and the complexity of the infrared spectrum indicate a structure similar to Co4(CO)i2 with the nickel in the basal plane171). 

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