Initiator dianionic

The disodium salt of diphenylacetylene dianion is stable in THE solution at -78°C. Methanol acts as a proton source toward the salt and causes the formation of a mixture of 1,2-diphenylethane with diphenylacetylene and small amounts of tran -stilbene (Chang and Johnson 1965, 1966). It seems logical that the reaction between (PhC=CPh) , 2Na and MeOH leads at first to PhCH=CHPh. The second step is supposed to consist of the further reduction of PhCH=CHPh at the expense of electrons from the nonreactedpartof the initial dianion. In principle, the electron transfer may proceed faster than the reaction of the initial dianion with protons. As a result, the diphenylacetylene dianion has to discharge into diphenylacetylene, whereas stilbene dianion has to form diphenylethane as follows ... 

Note that if these reagents are added to a lithium-initiated dianion, both ends of the chain will be capped with the functional group. Such chains are macro diacids or diols. Carboxyl- or hydroxyl-terminated chains may then participate in the usual step-growth... 

These reactions are usehil for the preparation of homogeneous difunctional initiators from a-methylstyrene in polar solvents such as tetrahydrofuran. Because of the low ceiling temperature of a-methylstyrene (T = 61° C) (26), dimers or tetramers can be formed depending on the alkaU metal system, temperature, and concentration. Thus the reduction of a-methylstyrene by sodium potassium alloy produces the dimeric dianionic initiators in THF (27), while the reduction with sodium metal forms the tetrameric dianions as the main products (28). The stmctures of the dimer and tetramer correspond to initial tail-to-tail addition to form the most stable dianion as shown in equations 6 and 7 (28). 

Aromatic radical anions, such as lithium naphthalene or sodium naphthalene, are efficient difunctional initiators (eqs. 6,7) (3,20,64). However, the necessity of using polar solvents for their formation and use limits their utility for diene polymerization, since the unique abiUty of lithium to provide high 1,4-polydiene microstmcture is lost in polar media (1,33,34,57,63,64). Consequentiy, a significant research challenge has been to discover a hydrocarbon-soluble dilithium initiator which would initiate the polymerization of styrene and diene monomers to form monomodal a, CO-dianionic polymers at rates which are faster or comparable to the rates of polymerization, ie, to form narrow molecular weight distribution polymers (61,65,66). 

For the mechanistic course of the reaction the diketone 5 is assumed to be an intermediate, since small amounts of 5 can sometimes be isolated as a minor product. It is likely that the sodium initially reacts with the ester 1 to give the radical anion species 3, which can dimerize to the dianion 4. By release of two alkoxides R 0 the diketone 5 is formed. Further reaction with sodium leads to the dianion 6, which yields the a-hydroxy ketone 2 upon aqueous workup ... 

The key step of the Cannizzaro reaction is a hydride transfer. The reaction is initiated by the nucleophilic addition of a hydroxide anion to the carbonyl group of an aldehyde molecule 1 to give the anion 4. In a strongly basic medium, the anion 4 can be deprotonated to give the dianionic species 5 ... 

Dicarboxylic acids have two dissociation constants, one for the initial dissociation i into a monoanion and one for the second dissociation into a dianion, i-or oxalic acid, H02C—COoH, the first ionization constant has p/Cal = 1.2 and the second ionization constant has pKa2 = 4.2. Why is the second carboxyl group so much less acidic than the first ... 

Group 4 metal complexes of the dianion [ BuNP( -N Bu)2PN Bu] polymerize ethylene in the presence of a co-catalyst, but they are readily deactivated [10,14]. This behaviour is attributed to coordination of the lone-pair electrons on the phosphorus(III) centers to Lewis acid sites, which initiates ring opening of the ligand [15]. 

SRNl substitution include ketone enolates,183 ester enolates,184 amide enolates,185 2,4-pentanedione dianion,186 pentadienyl and indenyl carbanions,187 phenolates,188 diethyl phosphite anion,189 phosphides,190 and thiolates.191 The reactions are frequently initiated by light, which promotes the initiating electron transfer. As for other radical chain processes, the reaction is sensitive to substances that can intercept the propagation intermediates. 

The mechanism of hydrolysis of o-carboxyaryl phosphates, whose dianions also hydrolyze much faster then, e.g., the phenyl phosphate monoanion 79,80) (maximum rate at about pH 4.8 and 25 °C 81)), was long a point of mechanistic contention. Thorough investigations81 led to proposal of a fast initial transprotonation... 

A mechanism proposed 87) for the alkaline hydrolysis of tetraethyl pyrophosphate, which is markedly accelerated by HPO e ions, has been substantiated by isotopic labeling 88). The nucleophilic attack by HPOJp on the symmetrical pyrophosphate 131 is considered to lead initially to the unsymmetrical P P1-diethyl pyrophosphate dianion 132 which decomposes spontaneously under the conditions of reaction to give the diethyl phosphate anion and POf 102. The latter reacts with water to form inorganic phosphate and with alcohols suclj as methanol and ethylene glycol to produce alkyl phosphates. 

In contrast to the allyl system, where the reduction of an isolated double bond is investigated, the reduction of extensively delocalized aromatic systems has been in the focus of interest for some time. Reduction of the systems with alkali metals in aprotic solvents under addition of effective cation-solvation agents affords initially radical anions that have found extensive use as reducing agents in synthetic chemistry. Further reduction is possible under formation of dianions, etc. Like many of the compounds mentioned in this article, the anions are extremely reactive, and their intensive studies were made possible by the advancement of low temperature X-ray crystallographic methods (including crystal mounting techniques) and advanced synthetic capabilities. 

The situation is even more complicated when a tris-electrophoric system is charged. The first question is which subunit will be charged initially. Then, if a dianion with the two electrons in separate electrophores has been formed, the charges can reside either on neighbouring electrophores or on those allowing the greatest possible distance between charges (see Fig. 1). 

Whitlock et al.14 discovered a reductive cyclization of enediynes promoted by lithium naphthalenide that provides substituted fulvenes and suggested a dianionic mechanism (Scheme 6). However, even now it is still unclear whether the enediyne dianion is indeed the cyclizing species or whether the initially formed acyclic radical-anion cyclizes first to give a fulvene radical-anion which is further reduced by lithium to give the cyclic dianion. 

Flash photolysis of the dianion of Roussin s Red Salt, [Fe2S2(NO)4]2, in particular the initial photoinitiated loss of NO (382) and the reverse recombination reaction, en route to the eventual product, the anion of Roussin s Black Salt, [Fe4S3(NO)7] , has been documented (383). A 4-RC6H4S group (R = H, Me, OMe, Cl, or CF3) replaces one of the chloride ligands in [Fe4S4Cl4]2 via a five-coordinated intermediate, with the detailed sequence of steps acid-dependent (384). Loss of chloride is... 

Reaction (I) involves the initial electron transfer from the metal to the monomer, which leads to the formation of a radical anion which could then participate in the reactions shown in (II) and (III), i.e., by coupling of two radical ions or by transfer of another electron from the metal, respectively, both processes leading to a dianionic species. 

This mechanism is based on initiation by electron-transfer which leads to a styrene radical anion, which couples rapidly due to its high concentration, and forms a dimeric styrene dianion that is capable of further propagation by anionic attack on styrene monomer. 

---