2.4.6- Triphenylphosphine, formation complexes

It was found [99JCS(PI )3713] that, in all cases, the formation of the deiodinated products 38 and 39 was accompanied by formation of the diynes 40 which were isolated in 60-90% yield. The authors believed that the mechanism of deiodination may be represented as an interaction ofbis(triphenylphosphine)phenylethynyl-palladium(II) hydride with the 4-iodopyrazole, giving rise to the bisftriphenylphos-phine)phenylethynyl palladium(II) iodide complex which, due to the reductive elimination of 1 -iodoalkyne and subsequent addition of alk-1 -yne, converts into the initial palladium complex. Furthermore, the interaction of 1-iodoalkynes with the initial alkyne in the presence of Cul and EtsN (the Cadiot-Chodkiewicz reaction) results in the formation of the observed disubstituted butadiynes 40 (Scheme 51). 

In pyridinium chloride ionic liquids and in l,2-dimethyl-3-hexylimida2olium chloride ([HMMIMjCl), where the C(2) position is protected by a methyl group, only [PdClJ was observed, whereas in [HMIMjCl, the EXAFS showed the formation of a bis-carbene complex. In the presence of triphenylphosphine, Pd-P coordination was observed in all ionic liquids except where the carbene complex was formed. During the Heck reaction, the formation of palladium was found to be quicker than in the absence of reagents. Overall, the EXAFS showed the presence of small palladium clusters of approximately 1 nm diameter formed in solution. 

Within the wide range of phosphorus compounds described as activating agents for polyesterification reactions,2,310 triphenylphosphine dichloride and diphenylchlorophosphate (DPCP) were found to be the most effective and convenient ones. In pyridine solution, DPCP forms a A-phosphonium salt which reacts with the carboxylic acid giving the activated acyloxy A -phosphonium salt. A favorable effect of LiBr on reaction rate and molar masses has been reported and assumed to originate from the formation of a complex with the A-phosphonium salt. This decreases the electron density of the phosphorus atom... 

A great variety of suitable polymers is accessible by polymerization of vinylic monomers, or by reaction of alcohols or amines with functionalized polymers such as chloromethylat polystyrene or methacryloylchloride. The functionality in the polymer may also a ligand which can bind transition metal complexes. Examples are poly-4-vinylpyridine and triphenylphosphine modified polymers. In all cases of reactively functionalized polymers, the loading with redox active species may also occur after film formation on the electrode surface but it was recognized that such a procedure may lead to inhomogeneous distribution of redox centers in the film... 

It is interesting to notice that the complex 58 is also able to react with soft donor hgands such as triphenylphosphine resulting in the formation in very mild conditions of the unexpected orthometallated complex 59 (Scheme 23) [89,91, 92]. The ligand here is linked to the metal through both an aromatic and an ylidic carbon. Other transformations are realized from 58 leading, including the compounds of the previous scheme, to four different structures for the bis-ylide (i) C,C-chelate (ii) C,C-orthometallated (iii) C,C-orthometallated and free ylide (iv) C,C,C-terdentate (Scheme 23). 

Mercaptans have been oxidized with diethyl azodicarboxylate and triphenylphosphine. It is suggested that the formation of a charge-transfer complex (57) may be a key step in the reaction. 

Polarographic studies are reported on thioesters, mainly of the type (140) and (141), and on trichloroethylphosphonites. In the field of nucleotides and nucleosides it is found that ATP has a very high surface activity at the mercury electrode, which is strongly dependent upon complex formation with transition metals. The polarographic behaviour of cobalt complexes with triphenylphosphine and its oxide has been studied in order to estimate extraction efficiencies. 

Nucleophilic Substitution of xi-Allyl Palladium Complexes. TT-Allyl palladium species are subject to a number of useful reactions that result in allylation of nucleophiles.114 The reaction can be applied to carbon-carbon bond formation using relatively stable carbanions, such as those derived from malonate esters and (3-sulfonyl esters.115 The TT-allyl complexes are usually generated in situ by reaction of an allylic acetate with a catalytic amount of fefrafcz s-(triphenylphosphine)palladium... 

Miscellaneous Reactions of Phosphines.- The role of chiral phosphines as ligands in the catalysis of reactions leading to the formation of chiral products has been reviewed.1111 A procedure for the determination of the enantiomeric excess in chiral phosphines has been developed, based on 13C n.m.r. studies of the diastereoisomeric complexes formed by phosphines with the chiral pinenyl nickel bromide complex. 111 Studies of the sulphonation of triphenylphosphine and of chiral arylphosphines have been reported in attempts to prepare water soluble ligands which aid... 

The analogous formation of aryl stannanes and aryl germanes from aryl halides occurs in the presence of catalytic amounts of palladium complexes of triphenylphosphine. Hexabutyl-... 

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