Iridium sulfide minerals

Mechanisms have been suggested for the N-bromosuccinimide (NBS) oxidation of cyclopentanol and cyclohexanol, catalysed by iridium(III) chloride,120 of ethanolamine, diethanolamine, and triethanolamine in alkaline medium,121 and for ruthenium(III)-catalysed and uncatalysed oxidation of ethylamine and benzylamine.122 A suitable mechanism has been suggested to explain the break in the Hammett plot observed in the oxidation of substituted acetophenone oximes by NBS in acidic solution.123 Oxidation of substituted benhydrols with NBS showed a C-H/C-D primary kinetic isotope effect and a linear correlation with er+ values with p = —0.69. A cyclic transition state in the absence of mineral acid and a non-cyclic transition state in the presence of the acid are proposed.124 Sulfides are selectively oxidized to sulfoxides with NBS, catalysed by ft-cyclodextrin, in water. This reaction proceeds without over-oxidation to sulfones under mild conditions.125... 

The platinum-group metals consist of ruthenium, rhodium, palladium, osmium, iridium, and platinum. Each of the metals occurs naturally in its native form, and in economically exploitable deposits the elements occur overwhelmingly as individual platinum-group mineral (PGM) species. Mutual substitution of the various PGE is common, but substitutions in other minerals, such as base-metal sulfides, typically occur to only a limited extent. A comprehensive review of PGM and PGE geochemistry is given by Cabri (2002). 

The platinum-group metals (Ru, Os, Rh, Ir, Pd and Pt) are rare (Figure 23.1) and expensive, and occur together either native or in sulfide ores of Cu and Ni. Three sites of mineral deposits in the former Soviet Union, Canada and South Africa hold the world s reserves. The main source of ruthenium is from wastes from Ni refining, e.g. from pentlandite, (Fe,Ni)S. Osmium and iridium occur in osmiridium, a native alloy with variable composition 15-40% osmium and 80-50% iridium. Rhodium occurs in native platinum and in pyrrhotite ores (Fei S, n = 0-0.2, often with <5% Ni). Native platinum is of variable composition but may contain as much as 86% Pt, other... 

Platinum has a certain tendency to form sulfides and arsenides, as for instance in the minerals cooperite PtS and sperrylite PtASj. The incHnation of platinum to form sulfides has the consequence that platinum often occurs with copper and nickel ores, especially pendandite. The metals are, however, mainly found as metallic phases, alloys with each other, with gold and with iron. The important alloy osmiridium with high contents of osmium and iridium also occurs in nature. 

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