Platinum complexes application

The generalized application of the aminolysis of halophosphanes has been the method of choice for the preparation of a wide variety of chiral phosphinous amides by starting from enantioenriched primary amines [36]. The aminolysis reaction occurs efficiently even when the halophosphane is placed in the coordination sphere of a metal, as in the palladium and platinum complexes of the type ds-M(Ph2PCl2)2Cl (M=Pd, Pt) [37,38]. 

Until recently, the hydroformylation using palladium had been scarcely explored as the activity of palladium stayed behind that of more active platinum complexes. The initiating reagents are often very similar to those of platinum, i.e., divalent palladium salts, which under the reaction conditions presumably form monohydrido complexes of palladium(II). A common precursor is (39). The mechanism for palladium catalysts is, therefore, thought to be the same as that for platinum. New cationic complexes of palladium that are highly active as hydroformylation catalysts were discovered by Drent and co-workers at Shell and commercial applications may be expected, involving replacement of cobalt catalysts. 

Chloroplatinic acid is used in preparing most platinum salts and complexes. It also is used as an electroplating bath for plating and coating of platinum. Other applications are in catalysis. 

The first experimental verification of these concepts in 1963 by the resolution of 124 through chiral platinum complexes 1371 was soon followed by the assignment of the chirality (—)(R) by an ingenious chemical correlation to a centrochiral compound, namely ( + )-tartaric acid138 . This was confirmed in 1970 by application of the Ryvoet-method to the platinum complex used for optical resolution 139), but is in contrast to an earlier prediction based on an optical model140). 

Recent applications of X/Y correlation techniques to measure chemical shifts of low- , spin-1/2 transition metal nuclei other than rhodium focused mainly on the analysis of silver and tungsten complexes in addition, the use of 13C-relayed H/195Pt correlations for the stereochemical analysis of some platinum complexes was explored.44 A report on the application of 31P/51V correlation spectroscopy demonstrated further the possibility of indirect detection of rapidly relaxing quadrupolar metal nuclei and the feasibility of the... 

The application of /( Q/ Pt relayed correlation spectroscopy for the characterisation of the thiourea-platinum complexes shown in Fig. 1544 may... 

A New Class of Hydrido-Bridged Platinum Complex with Application in Catalysis... 

Trofimenko also envisioned polypyrazolyl compounds of Be, Al, Ga, In, C, Si and P and prepared some alkane ligands and their complexes.1,2 A few other applications of polypyrazolylalkane ligands have been mentioned in passing in the sections dealing with cobalt and platinum complexes. The reactions of dipyrazolyl ketone to produce [Co(OC(pz)2)Cl2] and [Co(Me2C(pz)2)Cl2], the latter from acetone, are very unusual55 but do not seem to have been exploited further (Scheme 2). 

Ba[Pt(CN)4] is used in the production of fluorescent X-ray screens.94 Dichlorodihydroxy-diamine- and dichlorodinitratodiamine-platinum(IV) complexes show weak fungicidal activity, but there appears to be no likelihood of them actually being used to this end.95 Other applications of platinum complexes involve their use as anticancer agents, as selective stains in biology, in catalysis, in metallurgy and in photography, described in the relevant chapters of this volume. 

Resonance Raman spectroscopy, well known to be a sensitive probe of the nature of charge-transfer excited states, is now established to be a sensitive probe of intervalence states. In particular, onedimensional systems prove to be very amenable to study, and the results on a variety of linear-chain platinum complexes of both the Wolffram s red sort as well as the pop sort (pop = H2P2O52 ) are outlined. Brief mention is made of the application of resonance Raman spectroscopy to the study of electrochemically generated species. 

Coordination compounds have become very usable in medicine [361-364]. In this respect, use of metal complexes (mostly those of lanthanides) as diagnostic [365-367] and anticancer [368-370] media should be specially emphasized. Among the last complexes, the aminoplatinum-containing compounds play an important role, so the structural study of platinum complexes as a model of nucleobases [371] is a topic of renewed interest. The new issue of Comprehensive Coordination Chemistry II [372] contains a wide description of nanoparticles (vols. 6 and 7), biocoordination chemistry (vol. 8), and other aspects of application of coordination compounds. 

Little is known about the chemical nature of the recently isolated carbon clusters (C o> C70, Cg4, and so forth). One potential application of these materials is as highly dispersed supports for metal catalysts, and therefore the question of how metal atoms bind to C40 is of interest. Reaction of C o with organometallic ruthenium and platinum re nts has shown that metals can be attached directly to the carbon framework. Ihe native geometry of transition metal, and an x-ray difi action analysis of the platinum complex [(CgHg)3P]2Pt( () -C6o) C4HgO revealed a structure similar to that known for [(C4Hs)3P]2Pt( n -ethylene). The reactivity of C40 is not like that of relatively electron-rich planar aromatic molecules su( as benzene. The carbon-carbon double bonds of C40 react like those of very electron-deficient arenes and alkcnes. 

BINAP complexes have been used extensively in asymmetric synthesis, for example in hydrogenations,389,390 olefin isomerizations,390 arylation of olefins,391 and enantioselective allylation of aldehydes.392 Palladium or platinum complexes of (165) find important applications in enantioselective C—C bond formation,393-396 whilst iridium complexes are catalysts for the hydrogenation of nonfunctionalized tri- and tetrasubstituted olefins. 97... 

Within the context of toxicological and clinical importance, speciation studies have been focused on relatively few elements, mainly aluminum, antimony, arsenic, chromium, iodine, lead, mercury, platinum, selenium and tin. However, coupled HPLC-ICP-MS has most often been used for speciation of arsenic, selenium, iodine and, to a lesser extent, mercury. The primary species of these elements include different oxidation states, alkylated metal and/or metalloid compounds, selenoamino acids and selenopeptides.In addition, applications in smdies on the pharmacokinetics of metal-based drugs (mainly platinum complexes) and metalloproteins should be included. " In the following sections, the advances in speciation smdies of individual elements are reviewed. 

Stan s some one hundred articles dealt with the synthesis, structure, stereochemistry, and biological properties of coordination compounds, including the anticancer activity of platinum complexes optical rotatory dispersion circular dichroism the Pfeiffer Effect in metal complexes inorganic nomenclature and the application of computer techniques to chemical and information problems. A prominent educator, he edited three books on inorganic and coordination chemistry. 

Although many procedures for recovering platinum appear in the literature, they are not generally applicable to laboratory residues. Since those intended for ores assume the presence of other platinum metals, they are unnecessarily complicated. On the other hand, simpler methods involving only treatment with formaldehyde, formic acid, sodium dithionite, iron, magnesium, zinc, or other reducing agents reduce other inactive metals such as copper or silver. Furthermore, standard reduction methods are seldom directly applicable to the more stable platinum complexes. 

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