Ammine complexes transition metal

As described above, the catalytic activity of metal ion-exchanged zeolites for aniline formation has a good correlation with electronegativity and with the formation constant of ammine complexes of metal cations. The order of the activity agrees with the Irving-Williams order. These facts give irrefutable evidence that the transition metal cations are the active centers of the reaction. 

Cobalt exists in the +2 or +3 valence states for the majority of its compounds and complexes. A multitude of complexes of the cobalt(III) ion [22541-63-5] exist, but few stable simple salts are known (2). Werner s discovery and detailed studies of the cobalt(III) ammine complexes contributed gready to modem coordination chemistry and understanding of ligand exchange (3). Octahedral stereochemistries are the most common for the cobalt(II) ion [22541-53-3] as well as for cobalt(III). Cobalt(II) forms numerous simple compounds and complexes, most of which are octahedral or tetrahedral in nature cobalt(II) forms more tetrahedral complexes than other transition-metal ions. Because of the small stabiUty difference between octahedral and tetrahedral complexes of cobalt(II), both can be found in equiUbrium for a number of complexes. Typically, octahedral cobalt(II) salts and complexes are pink to brownish red most of the tetrahedral Co(II) species are blue (see Coordination compounds). 

W.W. Wendlandt and J.P. Smith, Thermal Properties of Transition Metal Ammine Complexes, Elsevier, Amsterdam, 1967. 

They based this modification on the known adsorbance of OH on glass and on the common occurrence of transition metal mixed water-ammonia complexes with coordination number of 4. Parallel stractural studies of the deposited CdS showed textured growth, supporting a mechanism whereby alternate Cd and S species were involved, in an ion-by-ion process. Such a growth suggests adsorption of a molecular hydroxy-ammine species rather than a cluster. In fact, the mechanism of Ortega-Borges and Lincot also does not differentiate between a hydroxide cluster and molecule. 

The reactions of chlorobenzene and benzaldehyde with ammonia over metal Y zeolites have been studied by a pulse technique. For aniline formation from the reaction of chlorobenzene and ammonia, the transition metal forms of Y zeolites show good activity, but alkali and alkaline earth metal forms do not. For CuY, the main products are aniline and benzene. The order of catalytic activity of the metal ions isCu> Ni > Zn> Cr> Co > Cd > Mn > Mg, Ca, Na 0. This order has no relation to the order of electrostatic potential or ionic radius, but is closely related to the order of electronegativity or ammine complex formation constant of metal cations. For benzonitrile formation from benzaldehyde and ammonia, every cation form of Y zeolite shows high activity. 

Jones and Landis (12) assumed the formation of the ammine complexes and their participation in the reaction of toluene with ammonia to form benzonitrile over a variety of transition metal-exchanged X zeolites. 

Room temperature emission has been observed for a number of transition metal complexes. Examples include Rh111 ammines,53 [Pt(CN)4]2-,54 and some Cu1 phosphine complexes.55 An important class is that of the polypyridine complexes of Ru11 and related species.56 This last emission, probably from a 3CT state, is quite strong and its occurrence has made possible a number of detailed studies of electron transfer quenching reactions. 

Coordination chemists are, however, generally interested in those systems with definite coordination numbers. The maximum coordination number is often achieved in a transition-metal ammine complex, especially where synthetic routes involve the use of excess ligand, as the gas, aqueous solution or the anhydrous liquid. Even so, forcing conditions or catalysts are required to form such complexes as Cu(NH3)62+ or Co(NH3)63+. 

Table 2 lists a selection given by Schlessinger.lul Naturally, these reflect complexes of relatively inexpensive central metal ions. An increasingly important use of transition metal ammines is in the stabilization and characterization of unusual anions, e.g. polyiodides (Table 1). 

More accurate force constants for a number of transition metal complexes with ammine ligands have been derived by normal-coordinate analyses of infrared spectra[130, 31l The fundamental difference between spectroscopic and molecular mechanics force constants (see Section 3.4) leads to the expectation that some empirical adjustment of the force constants may be necessary even when these force constants have been derived by full normal-coordinate analyses of the infrared data. This is even more important for force constants associated with valence angle deformation (see below). It is unusual for bond-length deformation terms to be altered substantially from the spectroscopically derived values. 

The only problem remaining in formulating say, ethylene platinous chloride (VI), was how the olefin attached itself to the transition metal atom. There were reports of ill-defined zinc- and aluminum-olefin complexes, and most chemists, if they thought of them at all, believed that olefin compounds, though much less stable and less numerous than the ammines, occurred just as widely. 

The heavier transition metal elements also form multinuclear ammine complexes, many with mixed oxidation states, for example, [Rn302(NH3)i4] + ( mtheninmred ) (48), [RU2(/aCl)3(NH3)6]2+ (49), [0S3(/xN)2(NH3)8(H20)6] + (50),... 

In spite of the many modern techniques available to the chemist, the known chemistry of polynuclear cobalt (III) complexes is essentially that deduced by Werner 60 years ago. Since his work, no new polynuclear cobalt complexes have been prepared and characterized and no new reactions uncovered. Modem work in this area is being aimed at attaining a better understanding of the electronic structures inherent in polynuclear ions, which would be of value in a variety of active fields. The chemistry of polynuclear complexes is important in such new areas as synthetic oxygen carriers, electron transfer reactions, and transition metal catalysis. The fact that these new investigations are solidly based on Werner s pioneer investigations testifies to the genius with which he opened up a new area of coordination chemistry, with only the simple chemical techniques available to him. His work in the area of polynuclear cobalt(III) ammine complexes should continue to serve as a model of solid research for some time to come. 

Fig. 12. Schematic diagram showing formation of aluminosilicate exchanged with transition metal ions or their ammine complex ions.

Additional alterations in the work terms with the electrode material for outer-sphere reactions may arise from discreteness-of-charge effects or from differences in the nature of the reactant-solvent interactions in the bulk solution and at the reaction plane. Thus metals that strongly chemisorb inner-layer solvent (e.g., HjO at Pt) also may alter the solvent structure in the vicinity of the outer plane, thereby influencing k bs variations in the stability of the outer-sphere precursor (and successor) states. Such an effect has been invoked to explain the substantial decreases (up to ca. 10 -fold) in the rate constants for some transition-metal aquo couples seen when changing the electrode materiaf from Hg to more hydrophilic metals such as Pt. Much milder substrate effects are observed for the electroreduction of more weakly solvated ammine complexes . 

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