Platinum complex thallium

Platinum complexes (continued) with aryls, thallium adducts, 3, 399 with bis(alkynyl), NLO properties, 12, 125 with bisalkynyl copper complexes, 2, 182-186 with bis(3,5-dichloro-2,4,6-trifluorophenyl), 8, 483 and C-F bond activation, 1, 743 in C-H bond alkenylations, 10, 225 in C-H bond electrophilic activation studies, 1, 707 with chromium, 5, 312 with copper, 2, 168 cyclometallated, for OLEDs, 12, 145 in diyne carbometallations, 10, 351-352 in ene-yne metathesis, 11, 273 in enyne skeletal reorganization, 11, 289 heteronuclear Pt isocyanides, 8, 431 inside metallodendrimers, 12, 400 kinetic studies, 1, 531 on metallodendrimer surfaces, 12, 391 mononuclear Pt(II) isocyanides, 8, 428 mononuclear Pt(0) isocyanides, 8, 424 overview, 8, 405-444 d -cP oxidative addition, PHIP, 1, 436 polynuclear Pt isocyanides, 8, 431 polynuclear Pt(0) isocyanides, 8, 425 Pt(I) isocyanides, 8, 425 Pt(IV) isocyanides, 8, 430... 

Secondly, Oberbeckmann-Winter et al. [90, 91] observed the formation of a cationic bimetallic species instead of the expected chloride abstraction when the benzylplatinum(II) complex depicted in Scheme 24 (bottom) was treated with thallium(I) hexafluorophosphate in dichloromethane. The starting platinum complex acted as a chelating metalloligand, coordinating to thallium via both the platinum atom and the aromatic ring. Again, exposure of the bimetallic intermediate to the more polar solvent acetonitrile released TlCl. 

A chloro(benzyl)platinum complex with an A,T-ligand having an oxazoline group 89 reacts with thallium hexa-fluorophosphate to produce complex 90, in which thallium is bonded at the apical position of the Pt center and is weakly bonded to the phenyl ring of the ligand (Equation (19)). ... 

The reaction is a sensitive one, but is subject to a number of interferences. The solution must be free from large amounts of lead, thallium (I), copper, tin, arsenic, antimony, gold, silver, platinum, and palladium, and from elements in sufficient quantity to colour the solution, e.g. nickel. Metals giving insoluble iodides must be absent, or present in amounts not yielding a precipitate. Substances which liberate iodine from potassium iodide interfere, for example iron(III) the latter should be reduced with sulphurous acid and the excess of gas boiled off, or by a 30 per cent solution of hypophosphorous acid. Chloride ion reduces the intensity of the bismuth colour. Separation of bismuth from copper can be effected by extraction of the bismuth as dithizonate by treatment in ammoniacal potassium cyanide solution with a 0.1 per cent solution of dithizone in chloroform if lead is present, shaking of the chloroform solution of lead and bismuth dithizonates with a buffer solution of pH 3.4 results in the lead alone passing into the aqueous phase. The bismuth complex is soluble in a pentan-l-ol-ethyl acetate mixture, and this fact can be utilised for the determination in the presence of coloured ions, such as nickel, cobalt, chromium, and uranium. 

There are many examples of platinum(II) interacting with metals such as lead(II) or thallium(I) but few where the same metals interact with platinum(O). Catalano et al. have reported a series of metallocryptands such as the one shown in (11) that act as hosts for thallium(I)72 and lead(II).73 They have also reported an unsupported thallium(I) interaction with the platinum in [Pt(PR3)3] (R = Ph or R3 = Ph2py).74 The Pt Tl separations in the cryptands (2.791-2.795 A) are slightly shorter than those in the unsupported complexes (2.865-2.889 A).72,74... 

Thallium(i) Derivatives of Nickel, Palladium, Platinum, and Gold Coordination Complexes 395... 

Table 14 Palladium, platinum, and gold coordination complexes that bind thallium...

Thallium Adducts of Arylplatinum and -gold Complexes 3.08.9.5.1 Platinum aryl complexes... 

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. 

Recently, the formation, structure, equilibrium, and kinetics of a family of cyano compounds containing a direct and not supported by ligands platinum-thallium metal-metal bond have been reported. The complexes are synthesized according to the reaction ... 

A similar model for the case of thallium cuprate is complicated by the large number of parameters that affect the state of the system, and also by the necessity to introduce two experimentally unknown quantities simultaneously into the model. However, taking into account the character of the pH dependences of all the processes that occur with the participation of thallium and copper, one can suppose that the shape of the thallium cuprate stability region would be close to that for the mixed oxide. That is, its width would increase with increasing concentration of copper ions (hydroxo complexes) within the crystallization zone. Although the crystallization process took place under a fortiori non equilibrium conditions, the results of the preparative analysis agree qualitatively with the concept of stability of the products. The interval over which formation of thallium cuprate on copper substrates occurs and the formation of the mixed oxide on platinum and carbon substrates can be observed is wider for higher values of the pH [352-354]. 

Cyclopropane formation can be dramatically enhanced by addition of Ai,iV,Af, A -tetrame-thylethylenediamine as an additional ligand or cosolvent. This was first reported in stoichiometric conversions of 7r-allylpalladium complexes and can also be applied to palladium-catalyzed processes." Thus allyl bromides with ketene acetals in the presence of thallium(I) acetate and 7i-allylpalladium(II)(TMEDA) acetate as catalyst gives cyclopropanes 9 with trans geometry of the substituents." " Similar results are observed with platinum catalysts vide infra). 

Studies have been continued by Glaser and his co-workers on platinum-thallium clusters. Very large 7ptxi couplings ranging from 48 to 66 kHz have been observed by them for [(NC)5PtTl(en) i] ( = 1-3) complexes where en denotes ethylenediamine. 

The trimethylsilylated silicic acids formed in this instance are soluble in conventional organic solvents, and their volatility is sufficiently high for them to be analysed by gas chromatography. Carzo and Hoebbel [411] carried out a comprehensive study of the chromatographic retention of various trimethylsilylated silicic acids on different stationary phases Apiezon L and silicone OV-1 and OV-17. The analysis of metals in the form of volatile complexes continues to attract attention, and have been described for analysing sodium [412], potassium [412], radium [413], caesium [413], barium [414], calcium [414], strontium [415], beryllium [416, 417], magnesium [418], zinc [419, 420], nickel [419], mercury [421], copper [422, 423], silver [424, 425], cadmium [421], indium [426, 427], g ium [428], scandium [217], cobalt [421], thallium [426], hafnium [429, 430], lead [431, 432], titanium [430], vanadium [433], chromium [434-436], manganese [426], iron [437], yttrium [438], platinum [439,440], palladium [439, 441, 442], zirconium [430], molybdenum [443], ruthenium [444], rhodium [445], rare earths [446—449], thorium [221, 450, 451] and uranium [221, 452]. The literature on GC analysis of metal chelates was reviewed by Sokolov [458]. 

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