Dissociative substitution reactions methods

I propose to develop and apply such methods, based on ultrafast X-ray absorption spectroscopy, to study the ultrafast molecular motions of organometallics in solutions. In particular, initial studies will focus on photo-induced ligand dissociation and substitution reactions of transition metal carbonyls and related compounds in various solvent systems. 

A useful method to probe whether the reaction mechanism involves an associative or dissociative pathway is to measure AV (the volume of activation) for the reaction. High pressure kinetics in methanol give AV 1 —12 cm3 mol-1 for an associative first step, and +7.7 cm3 mol"1 for the isomerization reaction. It is proposed that the faster reaction is a solvolytic replacement of Cl" followed by a dissociative isomerization step with [PtR(MeOH)(PEt3)2]+ (R = alkyl, aryl equation 210).580 Since isomerization and substitution reactions are mechanistically intertwined, it is useful to note here that for the rates of substitution of both cis- and frara,-PtBr(2,4,6-Me3C6H2)(PEt3)2 by I" and thiourea, the volumes of activation are negative, in support of associative processes.581 Further support for associative solvation as the first step in the isomerization of aryl platinum(II) complexes has been presented,582 and the arguments in favor summarized.583... 

As in the previous case, the cryoscopic method does not enable to determine whether Ti is bound in a complex anion (e.g. in TiF4Cl2 as proposed by Janz et al. (1958)) and, therefore, it is written as TiF4. However, from the experimental results it can be concluded that in molten NaCl and KCl, no substitution reaction occurs between Tip4 and Cl anions. On the other hand, the value of the correction factor in molten LiCl (r = 9) indicates that in this solvent titanium fluoride reacts with the chloride ions, thus increasing the number of new particles to 9, and the reaction can be interpreted by the dissociation scheme... 

The situation is considerably different for the iron(III) analog (TPPS)Fe "(H20)2 which is hexacoordinate in aqueous solution. In this case the reaction with NO is considerably slower (kon = 4.5 x 10 s ) and kojr (500 s ) is sufficiently large to be measurable by the flash photolysis method as well [92]. Temperature and hydrostatic pressure effects were probed and AH, AS and AV values of 69 + 3 kj mol , 95 10 J mol K and +9+1 cm mol were determined for the "orf reaction and 76 + 6 kJ mol , 60 + 11 ) mol and 18 + 2 cm mol respectively, for the off reaction [93j. The activation parameters for the on reaction compare very favorably with those measured for exchange between coordinated and solvent water for aqueous solutions of (TPPS)Fe "(H20)2 [94] and indicate that kinetics for the reaction of NO with this complex are dominated by the lability of the coordinated water. Furthermore, the large and positive values of AVj and ASj point to a dissociative substitution mechanism as described in Eq. (6.43). 

Dickert et al [Di 71, Di 72, Di 74] employed pressure jump and other relaxation methods to study the kinetics of the formation and dissociation reactions of various nickel complexes. They established that the substitution reactions of some of the nickel(II) complexes (taking place according to the following equation) varied linearly with the donicity of the solvent ... 

Because dissociation of CO from many metal-carbonyl complexes is slow, methods for ffie catalytic or stoichiometric assistance of ligand substitution reactions have received considerable attention. These methods are presented in ffie following sections. 

Reactions in Water.—A preliminary report has indicated that the rate of water exchange in the five-co-ordinate Co complex of (7) is particularly low for this metal (4.2 X 10 s at 25 °C) the activation parameters are given as A/f = 36.5 1.4 kJ mol and AS = — 34 4 JK mol. A preliminary application of conductometric pulse radiolysis to the dissociation of Co -amine chlorides has yielded results consistent with those obtained by other methods. The very small effect exerted by nickel(ii)-bound pyridine on the lability of the remaining water molecules has already been mentioned. An interesting preliminary report has indicated that the substitution reactions of Cu complexes are relatively slow in the absence of Jahn-Teller distortions [as, for example, in the trigonal-bipyramidal complex with (8) see Table 7]. 

Finally, we will only mention the ultrasonic absorption relaxation method which is, in fact, several different experimental techniques that permit the determination of relaxation times in the range 10 to 5 X 10 sec. Several of the dissociation field effect results in Table II have been confirmed by this method, and much new data on ligand substitution of alkali metal complexes have also been acquired by ultrasonic techniques (Eigen, 1963). Eigen and Tamm (1962) have thoroughly reviewed the role these techniques have played in revealing the mechanism of fast consecutive substitution reactions in metal complexes. 

The decarboxylation reaction usually proceeds from the dissociated form of a carboxyl group. As a result, the primary reaction intermediate is more or less a carbanion-like species. In one case, the carbanion is stabilized by the adjacent carbonyl group to form an enolate intermediate as seen in the case of decarboxylation of malonic acid and tropic acid derivatives. In the other case, the anion is stabilized by the aid of the thiazolium ring of TPP. This is the case of transketolases. The formation of carbanion equivalents is essentially important in the synthetic chemistry no matter what methods one takes, i.e., enzymatic or ordinary chemical. They undergo C—C bond-forming reactions with carbonyl compounds as well as a number of reactions with electrophiles, such as protonation, Michael-type addition, substitution with pyrophosphate and halides and so on. In this context,... 

The extraction system which was measured by the HSS method for the first time was the extraction kinetics of Ni(II) and Zn(II) with -alkyl substituted dithizone (HL) [14]. The observed extraction rate constants linearly depended on both concentrations of the metal ion [M j and the dissociated form of the ligand [L j. This seemed to suggest that the rate determining reaction was the aqueous phase complexation which formed a 1 1 complex. However, the observed extraction rate constant k was not decreased with the distribution constant Kj of the ligands as expected from the aqueous phase mechanism. 

Smooth COSMO solvation model. We have recently extended our smooth COSMO solvation model with analytical gradients [71] to work with semiempirical QM and QM/MM methods within the CHARMM and MNDO programs [72, 73], The method is a considerably more stable implementation of the conventional COSMO method for geometry optimizations, transition state searches and potential energy surfaces [72], The method was applied to study dissociative phosphoryl transfer reactions [40], and native and thio-substituted transphosphorylation reactions [73] and compared with density-functional and hybrid QM/MM calculation results. The smooth COSMO method can be formulated as a linear-scaling Green s function approach [72] and was applied to ascertain the contribution of phosphate-phosphate repulsions in linear and bent-form DNA models based on the crystallographic structure of a full turn of DNA in a nucleosome core particle [74],... 

For the synthesis of carbohydrate-substituted block copolymers, it might be expected that the addition of acid to the polymerization reactions would result in a rate increase. Indeed, the ROMP of saccharide-modified monomers, when conducted in the presence of para-toluene sulfonic acid under emulsion conditions, successfully yielded block copolymers [52]. A key to the success of these reactions was the isolation of the initiated species, which resulted in its separation from the dissociated phosphine. The initiated ruthenium complex was isolated by starting the polymerization in acidic organic solution, from which the reactive species precipitated. The solvent was removed, and the reactive species was washed with additional degassed solvent. The polymerization was completed under emulsion conditions (in water and DTAB), and additional blocks were generated by the sequential addition of the different monomers. This method of polymerization was successful for both the mannose/galactose polymer and for the mannose polymer with the intervening diol sequence (Fig. 16A,B). 

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