Step-wise complexation

Fig. 3.8 Step-wise complexation of H+ in AN with water, indicated as a function of the free water concentration [24].

Potentiometry is also useful to study step-wise complex formations. As an example, we consider here the case in which ion X in inert solvent s is complexed step-wise with other solvents D [25] ... 

Using this method, the step-wise complex formation constants of cations with basic solvents and of anions with protic solvents have been determined in relatively inert solvents like AN [25], PC [26] and acetylacetone (Acac) [27]. The original objective of this study is to determine the step-wise formation constants... 

The approximate statistical distribution of unidentate ligands on TV sites is a special case of the hypothesis of step-wise complex formation that all the intermediate complexes ML occur in mixtures with 0 < /Tpreparatively separate) and imperfect (labile, equilibrating in solution) complexes. The latter suggestion is similar to the influence of Aristotle s principle of the excluded middle on a housewife when she declares that a given compound either is toxic or not. Though most of the reactions of iridium(III) are slower than the reactions of carbon compounds in organic chemistry, there is little doubt... 

Step-wise complexity constants Kn determined by ion exchange method and by potentiometric method [ 1],... 

It is more then a billion times more stable as the copper complex. Remarkable is also the favored formation of the 2 1 complex. Independent from the stoichiometric ratio of HIDP vanadyl salt we never could observe a 1 1 complex, contrary to the observation of a step-wise complex formation in the case of other metals. This is in sharp contrast to the complex formation of IDP with vanadylions. 

Recent developments m calorimetry have focused primarily on the calorimetry of biochemical systems, with the study of complex systems such as micelles, protems and lipids using microcalorimeters. Over the last 20 years microcalorimeters of various types including flow, titration, dilution, perfiision calorimeters and calorimeters used for the study of the dissolution of gases, liquids and solids have been developed. A more recent development is pressure-controlled scamiing calorimetry [26] where the thennal effects resulting from varying the pressure on a system either step-wise or continuously is studied. 

The mechanism of the cycloaddition reaction of benzaldehyde 2a with Danishefsky s diene 3a catalyzed by aluminum complexes has been investigated theoretically using semi-empirical calculations [14]. It was found that the reaction proceeds as a step-wise cycloaddition reaction with the first step being a nucleophilic-like attack of Danishefsky s diene 2a on the coordinated carbonyl compound leading to an aldol-like intermediate which is stabilized by interaction of the cation with the oxygen atom of the Lewis acid. The next step is the ring-closure step, giving the cycloaddition product. 

Even complex procedures can be automated, such as dialysis to clean up dirty samplers, solvent extraction, automatic distillation and on-hne UV digestion. Unhke the earlier AutoAnalyzer systems which use a purely step-wise autosampler, the TRAACS is fitted with a random-access sampler as standard. 

Reaction of the bis(allyl) titanium complexes 16 and 18 with aldehydes occurs in a step-wise fashion with intermediate formation of the corresponding mono (allyl) titanium complex containing the alcoholate derived from 4 and 5 as a ligand at the Ti atom. Then the mono(allyl)titanium complexes combine with a second molecule of the aldehyde. Both the bis (allyl) titanium complexes and the mixed mono(allyl)titanium complexes react with the aldehydes at low temperatures with high regio- and diastereoselectivities. Interestingly, control experiments revealed that for the reaction of the bis (allyl) titanium complexes with the aldehyde to occur the presence of Ti(OiPr)4 is required, and for that of the intermediate mono(allyl)titanium complexes the addition of ClTi(OiPr)3 is mandatory (vide infra). 

The data here related on the kinetics of the propylene polymerization and of the transfer processes and the studies of the catalysts carried out with C-labelled alkylaluminums, derive from a series of researches mostly carried out some time ago, when the knowledge of the mechanism of the considered catalytic processes was still rather limited. Nevertheless, it helped remarkably to know these new processes of anionic coordinated polymerization their true catalytic nature (which regard to a-TiCU) differentiates them from the more usual polymerization processes (radicalic) which, actually, are not catalytic. They substantially contributed to demonstrate that the anionic coordinated polymerization is a step-wise addition process in which each monomeric unit inserts itself into a metal carbon bond of the catalytic complex. 

The sensor for ion solvation was a silver wire for Ag+ and an univalent cation-sensitive glass electrode for Li+ and Na+. In detennining AG (M+, R -> S) from Eq. (6.13), they assumed that the LJPs at PC/(PC + DMSO) and PC/DMSO were negligible (Ej = 0). At the same time, they detennined in PC the step-wise formation constants (/ ) for the complexation of Ag+, Li+ and Na+ with DMSO (see Section 6.3.3), and used them to calculate the Gibbs energies of transfer of those ions from PC to (PC + DMSO) and to neat DMSO. Equations (6.14) and (6.15) were used in the calculation ... 

During the course of our studies (30-32) of the synthesis and structures of rhodium acetylide and hydrido-acetylide complexes, we developed (32) a step-wise route to rrans-bis(acetylides) of the general form mer-rra/tf-[Rh(PMe3)3(H)(C=CR) (OCR )]. Unfortunately, scrambling processes have thus far precluded the preparation of the unsymmetrically substituted complexes (R R ) in the absence of... 

In (39), we have an example of a stereospecific formation of a pyrazo-line. When pyrazolines are photolyzed, the elimination of nitrogen, if concerted, should be syn. This stereospecific product has been observed (McGreer and Wu, 1967). The pyrolysis of pyrazolines, if concerted, should be anti. It is not clear why this process turns out to be complex in (39), one alkene is formed stereospecifically by an anti hydrogen migration, but two isomeric cyclopropanes are formed. Crawford and Ali (1967), find rather different product patterns in the pyrolysis of 3-methyl and 3,4-dimethylpyrazolines, and give evidence for diradical intermediates. The general problem of unstable intermediates in a step-wise process will be discussed in a later section. 

In search of model systems for iron hydrogenases, Sellmann et al. (67) investigated the interaction of I e(hdt)2 2 with H+, H2, and H . Formation of H2 was observed in the reaction with H+. The reaction mechanism was proposed to follow a step-wise protonation, forming a thiol-hydride complex and H2 is proposed to form via heterolytic elimination from the metal hydride species (Scheme 6). Theoretical calculations suggest that concerted H2 elimination from a dithiol species is thermally forbidden (67). 

---