Platinum complexes syntheses

Hetero-Diels—Alder reactions, via cobalt(III) complexes, 7,44 Heterodienes, with iron, 6, 145 if- Heterodienes, with tantalum, 5, 176 Heterodinuclear iridium complexes, synthesis, 7, 371 Heterodinuclear iridium—platinum complexes, synthesis and characterization, 7, 380... 

The only prominent antitumor tetravalent platinum complex so far is iproplatin (102). In vitro it has been shown to cause interstrand DNA-breaking and cross linking. Free radical scavengers inhibit these effects. The complex is less neurotoxic and less nephrotoxic than cisplatin. Its synthesis begins with hydrogen peroxide oxidation of cis-dichlorobis(isopropvlamine) platinum (100) to the dimethylacetamide complex 101. The latter is heated in vacuum to liberate iproplatin [25]. 

Hydrogen cyanide reactions catalysts, 6,296 Hydrogen ligands, 2, 689-711 Hydrogenolysis platinum hydride complexes synthesis, 5, 359 Hydrogen peroxide catalytic oxidation, 6, 332, 334 hydrocarbon oxidation iron catalysts, 6, 379 reduction... 

DNA polymerases, 5, 1007 Trans effect, 1,16, 26, 315 metal complexes, 2, 705, palladium(II) amine complexes, 5, 1115 platinum complexes, 5, 353, 493 six-coordinate compounds. 1, 49 T ransestcrification metal alkoxide synthesis, 2, 340 Transferases zinc, S, 1002... 

Scheme 6 Synthesis of platinum disulfido complexes from zerovalent platinum complexes...

A novel chiral dissymmetric chelating Hgand, the non-stabiUzed phosphonium ylide of (R)-BINAP 44, allowed in presence of [Rh(cod)Cl]2 the synthesis of a new type of eight-membered metallacycle, the stable rhodium(I) complex 45, interesting for its potential catalytic properties (Scheme 19) [81]. In contrast to the reactions of stabihzed ylides with cyclooctadienyl palladium or platinum complexes (see Scheme 20), the cyclooctadiene is not attacked by the carbanionic center. Notice that the reactions of ester-stabilized phosphonium ylides of BINAP with rhodium(I) (and also with palladium(II)) complexes lead to the formation of the corresponding chelated compounds but this time with an equilibrium be-... 

Scheme 32 Synthesis and methanolysis of palladium/platinum complexes of [l,2,3]diazaphospholes...

Platinum complexes with chiral phosphorus ligands have been extensively used in asymmetric hydroformylation. In most cases, styrene has been used as the substrate to evaluate the efficiency of the catalyst systems. In addition, styrere was of interest as a model intermediate in the synthesis of arylpropionic acids, a family of anti-inflammatory drugs.308,309 Until 1993 the best enantio-selectivities in asymmetric hydroformylation were provided by platinum complexes, although the activities and regioselectivities were, in many cases, far from the obtained for rhodium catalysts. A report on asymmetric carbonylation was published in 1993.310 Two reviews dedicated to asymmetric hydroformylation, which appeared in 1995, include the most important studies and results on platinum-catalogued asymmetric hydroformylation.80,81 A report appeared in 1999 about hydrocarbonylation of carbon-carbon double bonds catalyzed by Ptn complexes, including a proposal for a mechanism for this process.311... 

The robustness and excellent turnover numbers of platinum complexes with terminal alkynes have made it the catalyst of choice for the synthesis of polymers and other macromolecular architechtures. Alkyne hydrosilylation with platinum has also served as a key element in the synthesis of dendrimers. Sequential reaction of an alkyne with HSiMeCl2 and lithiated phenylacetylene afforded the branching unit of a dendrimer synthesis which has been used to afford a large variety of structures at high generation.44,4411 441 ... 

Visser and Ramakers [6] liberated 465 by the action of 2-methylthiirene 1,1-dioxide on the bis(triphenylphosphane)platinum complex 469 (Scheme 6.96) and observed a dimer, probably 474, or several dimers. The synthesis of 469 was accomplished by dehydrobromination of 468b in the presence of bis(triphenylphospha-ne)(ethylene)platinum and was believed to proceed via the trapping of 465 by the platinum complex. Jones et al. [185] doubted this opinion and regarded the reversed sequence as more likely, that is, the complexation of 468b by (PPh3)2Pt followed by the dehydrobromination. 

---