Platinum isotopes

P. Tidemand-Petersson, Staggering of the Moments of Inertia of very Neutron-Deficient Platinum Isotopes, Phys. Lett. 78B 44 (1978). 

Precise measurement of isotope ratios can be obtained by comparing the yields of isotopic ions desorbing from a sample placed on a strongly heated filament that is generally made from platinum, tantalum, rhenium, or tungsten. 

Since detailed chemical structure information is not usually required from isotope ratio measurements, it is possible to vaporize samples by simply pyrolyzing them. For this purpose, the sample can be placed on a tungsten, rhenium, or platinum wire and heated strongly in vacuum by passing an electric current through the wire. This is thermal or surface ionization (TI). Alternatively, a small electric furnace can be used when removal of solvent from a dilute solution is desirable before vaporization of residual solute. Again, a wide variety of mass analyzers can be used to measure m/z values of atomic ions and their relative abundances. 

For organometailic compounds, the situation becomes even more complicated because the presence of elements such as platinum, iron, and copper introduces more complex isotopic patterns. In a very general sense, for inorganic chemistry, as atomic number increases, the number of isotopes occurring naturally for any one element can increase considerably. An element of small atomic number, lithium, has only two natural isotopes, but tin has ten, xenon has nine, and mercury has seven isotopes. This general phenomenon should be approached with caution because, for example, yttrium of atomic mass 89 is monoisotopic, and iridium has just two natural isotopes at masses 191 and 193. Nevertheless, the occurrence and variation in patterns of multi-isotopic elements often make their mass spectrometric identification easy, as depicted for the cases of dimethylmercury and dimethylplatinum in Figure 47.4. 

The isotope patterns for two simple organometallic compounds in the molecular ion region (a) dimethylmercury and (b) dimethylplatinum. The seven isotopes of mercury show clearly and appear quite different from the six isotopes of platinum. Since there are only two carbon atoms, the contribution from C is negligible. 

Elemental isotopic compositions (isotope ratios) can be used mass spectrometrically in a routine sense to monitor a substance for the presence of different kinds of elements, as with chlorine or platinum. It can also be used in a precise sense to examine tiny variations in these ratios, from which important deductions can be made in a wide variety of disciplines. 

Other elements have atoms that can have different ratios of protons to neutrons. Indeed, hydrogen actually consists of three types of atoms. All hydrogen atoms have the same number of protons (one for hydrogen), giving each a mass of 1 Dalton, but some atoms of hydrogen also contain one neutron in the nucleus as well as the proton (mass of 2 Da), while yet others have two neutrons with each proton (mass of 3 Da). Thus hydrogen has three naturally occurring isotopes of mass 1, 2, and 3 Da. Chemically, there are only small differences between the reactivities of the different isotopes for any one element. Thus isotopes of palladium aU react in the same way but react differently from all isotopes of platinum. 

The most commonly used catalysts are palladized charcoal or calcium carbonate and platinum oxide. For better isotopic purity, the use of platinum oxide may be preferred for certain olefins since the substrate undergoes fewer side reactions while being chemisorbed on the platinum surface as compared to palladium.Suitable solvents are cyclohexane, ethyl acetate, tetrahydrofuran, dioxane or acetic acid-OD with platinum oxide. 

C02-0051. Platinum has four stable isotopes whose mass numbers and percentages are 194, 32.9% 195,... 

In dimethylformamide solution, platinum exchange between Pt(en)Br2 and Pt(en)Br4 has been found to be light-sensitive and catalysed by bromide ions. In the absence of light, a value < 1.33 x 10" l.mole . sec was obtained for the observed rate coefficient (25 °C) from data obtained by the isotopic method (i95pt) separation using an ether precipitation of Pt(en)Br2. The bridge mechanism was thought to occur... 

More recently, the dissociation of ethanol was studied by SERS [Lai et al., 2008]. By employing isotopically labelled ethanol, it was found that C—C bond breaking already occurs at low potentials, resulting in chemisorbed CH and CO. Upon oxidation the CH fragments are converted to CO at a potential below that of CO oxidation, suggesting that, at least on platinum, the potential limiting step in the oxidation of the adsorbed C species is the oxidation of CO. 

For a comparison of experimental Mossbauer isomer shifts, the values have to be referenced to a common standard. According to (4.23), the results of a measurement depend on the type of source material, for example, Co diffused into rhodium, palladium, platinum, or other metals. For Fe Mossbauer spectroscopy, the spectrometer is usually calibrated by using the known absorption spectrum of metallic iron (a-phase). Therefore, Fe isomer shifts are commonly reported relative to the centroid of the magnetically split spectrum of a-iron (Sect. 3.1.3). Conversion factors for sodium nitroprusside dihydrate, Na2[Fe(CN)5N0]-2H20, or sodium ferrocyanide, Na4[Fe(CN)]6, which have also been used as reference materials, are found in Table 3.1. Reference materials for other isotopes are given in Table 1.3 of [18] in Chap. 1. 

The two Mossbauer levels of Pt, 99 keV and 130 keV, are populated by either EC of Au(fi/2 = 183 days) or isomeric transition of Pt(fi/2 = 4.1 days). Only a few authors, e.g., [323, 324] reported on the use of Pt, which is produced by thermal neutron activation of " Pt via " Pt(n, y) Pt. The source used in the early measurements by Harris et al. [322, 325] was carrier-free Au diffused into platinum metal. Walcher [326] irradiated natural platinum metal with deuterons to obtain the parent nuclide Au by (d, xn) reactions. After the decay of short-lived isotopes, especially Au(fi/2 = 6.18 days), Au was extracted with ethyl acetate, and the Au/Pt source prepared by induction melting. Buym and Grodzins [323] made use of (a, xn) reactions when bombarding natural iridium with... 

Early measurements of " Th were on seawater samples and Th was co-precipitated from 20-30 L of seawater with iron hydroxide (Bhat et al. 1969). This procedure may not recover all of the " Th in the sample, and an alpha emitting Th isotope (e g., °Th or Th) is added as a yield monitor. Following chemical purification of the Th fraction by ion exchange chromatography, the Th is electrodeposited onto platinum or stainless steel planchets. The planchets are then counted in a low background gas-flow beta detector to measure the beta activity and subsequently with a silicon surface barrier detector to determine the alpha activity of the yield monitor. The " Th activity is thus determined as ... 

Exchange reactions between bulk and adsorbed substances can be studied by on-line mass spectroscopy and isotope labeling. In this section the results on the interaction of methanol and carbon monoxide in solution with adsorbed methanol and carbon monoxide on platinum are reported [72], A flow cell for on-line MS measurements (Fig. 1.2) was used. 13C-labeled methanol was absorbed until the Pt surface became saturated. After solution exchange with base electrolyte a potential scan was applied. Parallel to the current-potential curve the mass intensity-potential for 13C02 was monitored. Both curves are given in Fig. 3.1a,b. A second scan was always taken to check the absence of bulk substances. 

Thus we shall be concerned with properties that furnish information about the nature of the ligands, the oxidation state of the metal, and the geometry of the field of ligands. Techniques such as radio-isotope tracer studies, neutron-activation analysis, and electron microscopy are powerful methods for locating a metal within constituents of the cell and are particularly suited to heavy-metal rather than organic drugs but since they do not provide information about the chemical environment of the metal they will not concern us here. After each section below we shall give an example, not necessarily from platinum chemistry, where the method has been used with success in biochemistry. 

Platinum-195 is the only magnetically active isotope of platinum, the natural abundance being 33.8%. The shift of a saturated solution of K2PtCl6 is in D20 defined as zero ppm. The total chemical shift range is huge, about 13,000 ppm (from -6000 to +7000 ppm ). 

Proportions of Isotopically Labeled Products from Isomerization of Hexanes over 0.2% Platinum /Alumina Catalyst at 273°C ... 

Farkas and Farkas (32) examined the kinetics of the exchange and hydrogenation of benzene catalyzed by platinized platinum foil at room temperature. The occurrence of isotope exchange was detected by the thermal conductivity technique. They reported (i) that the exchange reaction was only a little faster than hydrogenation and (ii) that exchange... 

The rearrangement of platinacyclobutanes to alkene complexes or ylide complexes is shown to involve an initial 1,3-hydride shift (a-elimina-tion), which may be preceded by skeletal isomerization. This isomerization can be used as a model for the bond shift mechanism of isomerization of alkanes by platinum metal, while the a-elimination also suggests a possible new mechanism for alkene polymerisation. New platinacyclobutanes with -CH2 0SC>2Me substituents undergo solvolysis with ring expansion to platinacyclopentane derivatives, the first examples of metallacyclobutane to metallacyclopentane ring expansion. The mechanism, which may also involve preliminary skeletal isomerization, has been elucidated by use of isotopic labelling and kinetic studies. 

This reaction is reversible on a platinized Pt electrode and radical formation is the key to reversibility. Nonelectrodic homolysis does not take place unless platinum black is present as catalyst. The evidence is based on considerable exchange between isotopic 210Pb-labeled PhgPb2 and Ph3PbN03 which only occurs in the presence of platinum black. A similar case has been shown for PhgSn25(). 

Rate and equilibrium constant data, including substituent and isotope effects, for the reaction of [Pt(bpy)2]2+ with hydroxide, are all consistent with, and interpreted in terms of, reversible addition of the hydroxide to the coordinated 2,2 -bipyridyl (397). Equilibrium constants for addition of hydroxide to a series of platinum(II)-diimine cations [Pt(diimine)2]2+, the diimines being 2,2 -bipyridyl, 2,2 -bipyrazine, 3,3 -bipyridazine, and 2,2 -bipyrimidine, suggest that hydroxide adds at the 6 position of the coordinated ligand (398). Support for this covalent hydration mechanism for hydroxide attack at coordinated diimines comes from crystal structure determinations of binuclear mixed valence copper(I)/copper(II) complexes of 2-hydroxylated 1,10-phenanthroline and 2,2 -bipyridyl (399). 

---