Platinum , substitution

An alloy of palladium and gold has been placed on the market under the name of Palan as a platinum substitute. It is claimed to be even... 

Alloys of palladium and gold have recently been recommended as platinum substitutes under the names of rhotanium (see p. 192) and palan. 

Cleavage of a C-C bond of methoxy- or siloxycyclopropane is mediated by [Pt(CH2=CH2)Cl2]2 to give a (3-platinum substituted ketone through concomitant R -O bond breaking [16,17]. 

Spectrum reproduced several related platinum substituted nitroxides reported. ) Spectrum reproduced incorrectly assigned in [70McCl]. ... 

The coordination of an isocyanide, followed by the migration of an adjacent group to give rise to a coordinated imine, is exemplified by three different examples, giving rise to complexes 116 and 117 and the stanna-/ /(9.r<9-dodecaborate complex 118. Platinum-substituted fulvenes can be prepared in a similar manner by attack of a coordinated isocyanide by the cyclopentadienyl anion. ... 

Catalysis. Platinum-catalyzed hydrosilation is used for cross-linking siUcone polymers and for the preparation of functionally substituted silane monomers (250). The most widely used catalyst is chloroplatinic acid (Spier s catalyst), H2PtCl3. Other compounds that catalyze the reaction include Pt(Il)... 

Platinum-group metals (qv) form complexes with chelating polymers with various 8-mercaptoquinoline [491-33-8] derivatives (83) (see Chelating agents). Hydroxy-substituted quinolines have been incorporated in phenol—formaldehyde resins (84). Stannic chloride catalyzes the condensation of bis(chloromethyl)benzene with quinoline (85). 

Isoquinoline can be reduced quantitatively over platinum in acidic media to a mixture of i j -decahydroisoquinoline [2744-08-3] and /n j -decahydroisoquinoline [2744-09-4] (32). Hydrogenation with platinum oxide in strong acid, but under mild conditions, selectively reduces the benzene ring and leads to a 90% yield of 5,6,7,8-tetrahydroisoquinoline [36556-06-6] (32,33). Sodium hydride, in dipolar aprotic solvents like hexamethylphosphoric triamide, reduces isoquinoline in quantitative yield to the sodium adduct [81045-34-3] (25) (152). The adduct reacts with acid chlorides or anhydrides to give N-acyl derivatives which are converted to 4-substituted 1,2-dihydroisoquinolines. Sodium borohydride and carboxylic acids combine to provide a one-step reduction—alkylation (35). Sodium cyanoborohydride reduces isoquinoline under similar conditions without N-alkylation to give... 

Several types of nitrogen substituents occur in known dye stmetures. The most useful are the acid-substituted alkyl N-substituents such as sulfopropyl, which provide desirable solubiUty and adsorption characteristics for practical cyanine and merocyanine sensitizers. Patents in this area are numerous. Other types of substituents include N-aryl groups, heterocycHc substituents, and complexes of dye bases with metal ions (iridium, platinum, zinc, copper, nickel). Heteroatom substituents directly bonded to nitrogen (N—O, N—NR2, N—OR) provide photochemically reactive dyes. 

The following compounds have been obtained from thiete 1,1-dioxide Substituted cycloheptatrienes, benzyl o-toluenethiosulfinate, pyrazoles, - naphthothiete 1,1-dioxides, and 3-subst1tuted thietane 1,1-dioxides.It is a dienophile in Diels-Alder reactions and undergoes cycloadditions with enamines, dienamines, and ynamines. Thiete 1,1-dioxide is a source of the novel intermediate, vinylsulfene (CH2=CHCH=SQ2). which undergoes cyclo-additions to strained olefinic double bonds, reacts with phenol to give allyl sulfonate derivatives or cyclizes unimolecularly to give an unsaturated sultene. - Platinum and iron complexes of thiete 1,1-dioxide have been reported. 

There are, however, technical limitations to substitution. Some materials are used in ways not easily filled by others. Platinum as a catalyst, liquid helium as a refrigerant, and silver on electrical contact areas cannot be replaced they perform a unique function - they are, so to speak, the vitamins of engineering materials. Others - a replacement for tungsten for lamp filaments, for example - would require the development of a whole new technology, and this can take many years. Finally,... 

In many applications tantalum can be substituted for platinum and gold, and there are some environments in which tantalum is more corrosion resistant than platinum. Table 3.37 lists the main chemicals for which tantalum is not a suitable substitute for platinum and, conversely, those for wliich tantalum is better than platinum. Tantalum is rapidly embrittled by nascent hydrogen even at room temperature. Therefore, it is very important to avoid the formation of galvanic couples between tantalum and other metals. 

Hydrogenation of unsubstituted or 3/ -substituted-A -steroids (25a) over platinum gives, almost exclusively, the 5a-product (26a). With 3a-substituents (25b) the 5j5-product (24b) is formed preferentially. Hydrogenation of A" -steroids (23a or b) gives product mixtures in which the 5a/5j5 ratio is dependent on the nature and stereochemistry of the sub-... 

Hydrogenation of 19-hydroxy-3a- and 3j5-substituted-A -steroids over platinum or rhodium yields increased amounts of 5j9-products as compared to the corresponding 19-desoxy series (hydroxyl group effect). In contrast, the A -19-carboxaldehyde (27) gives only the 5a-product when hydrogenated over either palladium or platinum. ... 

This method involves very simple and inexpensive equipment that could be set up m any laboratory [9, 10] The equipment consists of a 250-mL beaker (used as an external half-cell), two platinum foil electrodes, a glass tube with asbestos fiber sealed m the bottom (used as an internal half-cell), a microburet, a stirrer, and a portable potentiometer The asbestos fiber may be substituted with a membrane This method has been used to determine the fluoride ion concentration in many binary and complex fluondes and has been applied to unbuffered solutions from Willard-Winter distillation, to lon-exchange eluant, and to pyrohydrolysis distil lates obtained from oxygen-flask or tube combustions The solution concentrations range from 0 1 to 5 X 10 M This method is based on complexing by fluonde ions of one of the oxidation states of the redox couple, and the potential difference measured is that between the two half-cells Initially, each cell contains the same ratio of cerium(IV) and cerium(tll) ions... 

Because their rates of substitution tue convenient for study, most work has been done with platinum complexes, and for lhe.se it is found that ligands can be airanged in a fairly consistent order indicating their relative abilities to labilize ligands irans to themselves ... 

Emission spectra have been recorded for four aryl-substituted isoindoles rmder conditions of electrochemical stimulation. Electrochemiluminescence, which was easily visible in daylight, was measured at a concentration of 2-10 mM of emitter in V jV-dimethylformamide with platinum electrodes. Emission spectra due to electrochemi-luminescence and to fluorescence were found to be identical, and quantum yields for fluorescence were obtained by irradiation with a calibrated Hght source. Values are given in Table X. As with peak potentials determined by cyclic voltammetry, the results of luminescence studies are interpreted in terms of radical ion intermediates. ... 

It is known that tropylium may be prepared from tropylidene via hydride abstraction by PhgC or MegC carbonium ions therefore, it is very likely that here too the dehydrogenation is a hydride transfer from the 1,5-dione to an acceptor. A similar dehydrogenation of chromanones to chromones, with triphenylmethyl perchlorate was reported. A study of the electrooxidation of 1,5-diones on a rotating platinum electrode showed that 1,5-diaryl-substituted diones afford pyrylium salts in these conditions and that the half-wave potentials correlate with yields in chemical dehydrogenations. 

Organonickel derivatives also offer cases of the -coordination of the substituted hydrotrisfpyrazol- l-yl)borate ligand. For the palladium and platinum complexes, the M(II) M(IV) (M = Pd, Pt) transformation is facile. Organopalla-dium chemistry offers anew type of agostic interactions, C—H - - - Pd, where the C—H bond belongs to one of the pyrazolate rings. Cyclopalladation of various pyrazol-l-ylborates and -methanes does not modify their structure. 

Condensation of ethyl acetoacetate with phenyl hydrazine gives the pyrazolone, 58. Methylation by means of methyl iodide affords the prototype of this series, antipyrine (59). Reaction of that compound with nitrous acid gives the product of substitution at the only available position, the nitroso derivative (60) reduction affords another antiinflammatory agent, aminopyrine (61). Reductive alkylation of 61 with acetone in the presence of hydrogen and platinum gives isopyrine (62). Acylation of 61 with the acid chloride from nicotinic acid affords nifenazone (63). Acylation of 61 with 2-chloropropionyl chloride gives the amide, 64 displacement of the halogen with dimethylamine leads to aminopropylon (65). ... 

A substitute may be prepared thus 0 05 gram palladous chloride is placed in a special shaking flask with 50 c.c, of 50 per cent, alcohol and 1 or 2 c c. of 1 per cent, aqueous solution of gum-arabic, the weight of gum being about one-fourth the weight of the palladous chloride. On shaking this mixture in an atmosphere of hydrogen the chloride is reduced with formation of a black solution of colloidal platinum, which is rendered stable by the small quantity of gum present. 

The above generalities apply particularly to palladium. Hydrogenation over platinum or rhodium are far less sensitive to the influence of steric crowding. Reduction of 1-t-butylnaphthalene over platinum, rhodium, and palladium resulted in values of /ci//c2 of 0.42, 0.71, and 0.024, respectively. Also, unlike mononuclear aromatics, palladium reduces substituted naphthalenes at substantially higher rates than does either platinum or rhodium. For example, the rate constants, k x 10 in mol sec" g catalyst", in acetic acid at 50 C and 1 atm, were (for 1,8-diisopropylnaphthalene) Pd (142), Pt(l8.4), and Rh(7.1)(25). 

Extreme differences between 5% palladium-on-carbon and platinum oxide were found on reduction of the 5-aryl substituted oxazole 14. Over palladium, 15 was formed in quantitative yield by hydrogenolysis of the benzyl hydroxyl, whereas over Pt, scission of the oxazole occurred to give 13 quantitatively (48). Hydrogenation of 15 over platinum oxide gave the phenethylamide 16. 

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