Thallium complexes reactions

Cobaltocene is partially oxidized and in part undergoes insertion of a borylene group, RB. The borinato ligands derive from the unknown borabenzene ( 6.5.3.4). Some porphyrinatoindium and thallium complexes ( 6.5.2.2) can also be synthesized via oxidative addition reactions (TPP)InCl is added oxidatively to Co2(CO)g and Mn2(CO) to give (TPP)In—Co(CO)4 and (TPP)ln — Mn(CO)j, respectively, and (oep)InCl is added to CojfCOg to yield (oep)ln— 0(00)4. 

The potassium derivatives obtained from the reaction mixture are typically not isolated in pure form, and the crude products are often converted directly to the thallium complexes by metathesis with either thallium nitrate or thallium acetate [Eqs. (1) and (2)]. 

Thallium(i) salts have long been used in reactions with organic and organometallic halide complexes as a means of activating the halide by removal as insoluble T1X. However, the thallium ions proved not to be innocent bystanders, and numerous examples were reported in COMC (1995) where the metal-bound thallium complexes were formed. Deliberate reactions of thallium(i) and thallium(m) salts with metal carbonyl anions have yielded a variety of complexes of the form T1 MLJ3. In the past decade, new examples of metal carbonyl derivatives of thallium have been prepared (see Table 2). In addition, the propensity for Tl+ to form adducts with 16-electron noble metal complexes has been exploited. 

An example of this is the gold-thallium complex n[Au(CN)2] [69], prepared by reaction of T1N03 and K[Au(CN)2]-2H20 in the 90s by Patterson et al. This group carried out a pioneering study of the luminescence properties of this complex and their theoretical interpretation. The structure showed a complexity that made the analyses difficult. Thus, neutron diffraction studies showed thallium-gold interactions of 3.446 and 3.463 A, shorter than the sum of their van der Waals radii (3.62 A) in one of the three crystallographically-distinct Au sites in the crystal. 

The thallium complex 8 is available by two general routes involving the use of either T1(I) or Tl(III) salts. The former involves a disproportionation reaction [Eq. (1)] presumably via a... 

B. Supramolecular Gold-Thallium Complexes through Acid-Base Reactions... 

Although LiPor-precursors are involved in the synthesis, ate complexes of type MI[LnPor2] have not been isolated, in contrast to the pyrrol derivatives [197] or charge related M [Ln(COT)2] complexes [240]. However, ternary systems are readily available by reaction of the protonated form HLnPor2 with, e.g., M OR (Eq. 16). Structural evidence has been given for the thallium complex Tl[Pr(OEP)2] [228]. 

Phosphonate Arene Osmium(II) Complexes. Benzene osmium(II) phosphonates have been made via the initial reaction of phosphite-containing osmium cations of type 147 with Nal. Demethylation occurs, and the anionic complex 182 is obtained. Protonation with trifluoroacetic afforded adduct 183 which generated complex 184 on treatment with pyridine. The latter was shown to be a precursor of the thallium complex 185 containing the chelating osmium phosphonate 115). 

To employ this reaction as a spot test in the presence of other noble metals (gold, palladium, etc.), the platinum is fixed as thallium(I) hexachloro-platinate(IV), Tl2[PtCl6], which is stable to ammonia solution upon washing the precipitate with ammonia solution, the thallium complexes with gold, palladium, etc., pass into solution. 

The kinetic characteristics of ligand exchange of thallium complexes in solution have been little explored, in contrast to the numerous equilibrium studies (4-6,41,57,61,66,67,90,92,93,96,97,112,214-246) and a large number of studies of redox reactions involving thallium (81, 100, 103, no, 246-288). 

Far more surprising was the fact that the anation reactions constituted only a minor part of the chloride exchange in this chemical system. Instead, up to the Cl/Tl ratio 3, the dynamics is dominated by a direct ligand exchange between two thallium complexes. 

For the direct exchange between the thallium complexes, Eq. (9), the dissociatively activated reaction mechanism previously proposed for the thallium chloride system (169) could now be confirmed and... 

Thallium complexes amidines, 205 phthalocyanines, 863 porphyrins, 821 triazines, 205 Thallium(I) complexes hexafluoroacetylacetone, 372 Thallium III) complexes carboxylic acids reactions, 443 1,3-diketones synthesis, 377... 

The oxidation of methylcyclobutene by Hg" and Pd" in IM perchloric and hydrochloric acids has been described, and whereas the thallium(m) reaction involves an intermediate complex, the corresponding oxomercurial species is relatively stable. The products of oxidation and isomerization of phenylcyclopropane by palladium(n) have been reported. In 2 1 glyme-H20 (v/v) using PdCU " as oxidant, propiophenone and phenylacetone are the major products, the reaction proceeding via an oxypalladium complex,... 

Properties and Reactions.— The unstable thallium complex of the bilindione (73) is oxidized by air in methanol to a dimethoxy-derivative (74) the latter undergoes photo-oxidation to a tripyrrinone (75) and ethylmethyl maleimide. The... 

Thallium(III) acetate reacts with alkenes to give 1,2-diol derivatives (see p. 128) while thallium(III) nitrate leads mostly to rearranged carbonyl compounds via organothallium compounds (E.C. Taylor, 1970, 1976 R.J. Ouelette, 1973 W. Rotermund, 1975 R. Criegee, 1979). Very useful reactions in complex syntheses have been those with olefins and ketones (see p. 136) containing conjugated aromatic substituents, e.g. porphyrins (G. W. Kenner, 1973 K.M. Smith, 1975). 

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