Phosphorus reaction with indium

The rather complicated indium-phosphorus cluster framework 24 was obtained by the reaction of indium(III) chloride with PhP(SiMe3)2 in the presence of triethyl-phosphane [Eq. (12)] [29]. Apparently, a complex redox process occurred, in the course of which phosphorus atoms were oxidized by the formation of three P-P bonds, while six indium atoms were reduced from +3 to +2 accompanied by the formation of three In-In bonds. The In-In (average 274 pm) and P-P bond lengths (average 222 pm) represent localized single bonds. Other strategies for the... 

Ru(OH)Cls] - + 3H2O + 103 where the rate-determining step is the reduction of ruthenium(iv) by the amine with rapid re-oxidation of the metal complex by the oxidant. The oxidation of iodide by isopolymolybdic acids in the presence of germaniumfiv) and phosphorus(v) has been reported, the two-stage reactions involving the formation of a Ge " (or P ") complex with the molybdate, followed by a secondary reaction of this intermediate with I to yield the blue heteropolyacid. The two-electron reaction of indium(i) with tri-iodide ions,... 

Although in this chapter we shall be restricting coverage to reactions of transition-metal complexes, the phenomenon of oxidative addition is not confined to this type of compound. Such reactions are also well established for non-transition metals—a recently reported example concerns the oxidative addition of methyl bromide to indium(i) bromide to give InBr2Me— and for non-metals, as in the reaction of phosphorus trichloride with chlorine, to cite a very familiar example. Likewise, reductive eliminations are known and studied outside the area of transition-metal complexes. One example has been mentioned in Chapter 1 of Part II of this volume, namely the elimination of alkyl halides from the thallium(iii) compounds TlRXa. ... 

Iseler, G. W. et al., Int. Conf. Indium Phosphide Relat. Mater., 1992, 266 Reaction of beryllium, copper, manganese, thorium or zirconium is incandescent when heated with phosphorus [1] and that of cerium, lanthanum, neodymium and praseodymium is violent above 400°C [2], Osmium incandesces in phosphorus vapour, and platinum bums vividly below red-heat [3], Red phosphorus shows very variable vapour pressure between batches (not surprising, it is an indeterminate material). This leads to explosions when preparing indium phosphide by reactions involving fusion with phosphorus in a sealed tube [4],... 

Other main group elements have been used as promoters in MCS beds containing copper, tin and zinc. Phosphorus and indium have been used in the MCS reaction. The reaction of silicon (40 g) with MeCl (2 bar) at 300 °C in the presence of Cu (3.2 g), ZnO (0.05 g), In (0.004 g) and P (0.056 g) gave 1.7% of Me3SiCl, 0.017% mixture of MeSiCl3/Me2SiCl2 and 3.7% of polysilanes34. Antimony, just below phosphorus in... 

The dilFerence in these reorganization energies cannot wholly account for the variation of /-- 12kcal in the heats of addition reactions. This variation must be, in part, due to a weaker o-bond between phosphorus and boron atoms than between nitrogen and boron atoms. This can be shown from the heats of addition reactions between gallium trimethyl and either trimethylamine or tri-methyl pho sphine. These heats are shown in Table 7, together with similar data for indium trimethyl. 

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