Mercury platinum complexes

Kouwenhoven (6) sjmthesised two bis-olefinic ligands related to the simple pent-4-enyl compounds mentioned above. These were of the general formula PhD[(CH2)aCH =CH2]2 (D = P, As) and formed platinum(II) and mercury(II) complexes. The platinum complexes LPtCla (L = PhD[(CH2)3 CH=CH2]2) were found to be monomeric species containing, as shown by their i. r. spectra, one coordinated and one free double bond. The two mercury complexes [LHgClaJs did not contain coordinated olefinic groups. 

CsHuN, Ethanamine, A-ethyl-A-methyl-tungsten complex, 26 40, 42 C6HF5, Benzene, pentafluoro-gold complexes, 26 86-90 C H4I2, Benzene, 1,2-diido-iridium complex, 26 125 CJT, Phenyl platinum complex, 26 136 C,H,N, Pyridine osmium complex, 26 291 OHtS, Benzenethiol osmium complex, 26 304 QH7P, Phosphine, phenyl-cobalt-iron complex, 26 353 QH 1-Butyne, 3,3-dimethyl-mercury-molybdenum-ruthenium complex, 26 329-335 C6H 4P, Phosphine, triethyl-platinum complex, 26 126 platinum complexes, 26 135-140 CsHisPO, Triethyl phosphite iron complex, 26 61... 

In the majority of catalytic reactions discussed in this chapter it has been possible to rationalize the reaction mechanism on the basis of the spectroscopic or structural identification of reaction intermediates, kinetic studies, and model reactions. Most of the reactions involve steps already discussed in Chapter 21, such as oxidative addition, reductive elimination, and insertion reactions. One may note, however, that it is sometimes difficult to be sure that a reaction is indeed homogeneous and not catalyzed heterogeneously by a decomposition product, such as a metal colloid, or by the surface of the reaction vessel. Some tests have been devised, for example the addition of mercury would poison any catalysis by metallic platinum particles but would not affect platinum complexes in solution, and unsaturated polymers are hydrogenated only by homogeneous catalysts. 

The term 7r,7r-transfer has been proposed for 7r-allyl ligand transfer from one transition metal to another. Such processes differ from those giving a-allyl derivatives 160), which are termed Tr.a-transfer processes. The latter have been studied in detail 161) for 7r-allylnickel, -palladium, and -platinum complexes interacting with metallic mercury. It has been shown that binuclear 7r-allylpalladium complexes rapidly react with mercury in... 

The same study describes the reaction of bis(7r-allyl)palladium and -platinum complexes with metallic mercury 161). 

CF3H, Methane, trifluoro-cadmium complex, 24 55 mercury complex, 24 52 CF3NOS, Imidosulfurous difluoride, (fluorocarbonyl)-, 24 10 CH2, Methylene ruthenium complex, 25 182 CH2CI4P2, Phosphine, methylenebis-(dichloro)-, 25 121 CH3, Methyl cobalt complexes, 23 170 mercury complexes, 24 143-145 platinum complex, 25 104, lOS CNO, Cyanato silicon complex, 24 99 CN2OS2, l,3k, 2,4-Dithiadiazol-5-one, 25 53 CO, Carbon monoxide chromium complexes, 21 1, 2 23 87 cobalt complex, 25 177 cobalt, iron, osmium, and ruthenium complexes, 21 58-65 cobalt-osmium complexes 25 195-197 cobalt-ruthenium cluster complexes, 25 164... 

Conversion of norbornadiene to nortricyclenes can also be achieved with organomercurials. This reaction proceeds via transmetalation to form a c-bonded organopalladium system which inserts norbornadiene. Thus an enrfo-cw-addition is observed. Conversions of this type were observed in the phenylation of dichloro(t -norbornadiene)palladium either with diphenyl-mercury or, more conveniently, with sodium tetraphenylborate to give di-/r-chlorobis(2 5,6-t -c ffo-3-phenylbicyclo[2.2.1]hept-e /o-2-yl)palladium (30) via cis addition.By contrast, the analogous platinum complex did not give a phenylation product. The palladium complex 30 underwent reversible ring closure to a nortricyclenyl complex 31 with pyridine. ... 

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. 

The equilibrium of benzoselenazole (4) with gold(III) <91JCS(D)307>, zinc, cadmium, and mercury was studied <81ZAAC(478)233>. The nitrogen of benzoselenazoles reacts with platinum bromide to form the platinum complex (see Section 3.08.12). 

Organomercurials can also be used for the synthesis of alkyl complexes. Organomercurials have stable alkyl-mercury bonds, and the alkyl groups can be transferred to transition metal complexes (alkylation of the transition metal complexes). Thus diphenylmercury reacts with one equivalent of dichloroplat-inum complex to produce phenylmercuric chloride and monosubstituted platinum complex in good yield 73). 

Several systems for selective catalytic reactions based on Shilov s system have been developed with oxidants more practical than platinum(IV). Periana reported two different systems for the oxidation of methane in sulfuric acid containing SO,. One of the catalysts is a simple mercuric halide, and reactions catalyzed by this mercury compound generated methyl sulfate with turnover frequencies of 10" s" . The second system is more reactive and is based on a platinum complex containing a bipyrimidine ligand (Equation 18.7). In this case, methane is converted to methyl bisulfate with 81% selectivity, greater than 500 turnovers, and a turnover frequency of 10 s" . These reactions are selective for the functionalization of methane to this methanol derivative because the electron-withdrawing... 

Furthermore, two-photon fluorescence microscopy was used to show that a cyclometalated platinum(II)-rhodamine complex 11 can act as a selective indicator for mercury(II) ions in aqueous solution, including when incubated in cells (Fig. 11). Luminescent cyclometalated platinum complexes were also designed for potential in photodynamic therapy, with a 2-(2 thienyl)polypyridyl complex synthesised by Selke et al. displaying potent photoactivity and localisation in mitochondria and the nucleus. ... 

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