Reactions with Other Metals

In contrast to previous reports (see Fluor Erg.-Bd. 1,1959, p. 245), zinc powder does not react with NF3 when rapidly heated in an NF3 atmosphere (20°C per minute in a differential scanning calorimeter) until about 300°C. Successive heating of the same sample apparently passivates the surface so that no reaction takes place at 300°C [17]. 

The rate constant for HgF(B) formation, k = 8.1x10 cm -molecule -s (corresponding to the cross section o = 23.3 A ), was measured using a flowing afterglow technique [3]. 

The reaction of samarium and NF3 shows strong chemiluminescence. The emission results from excited SmF molecules and Sm atoms. The highest photon yield measured (for the definition, see the AI + NF3 reaction) was 70% at 2.3 Torn About 12% of the reaction exothermi-city was converted into radiation [8]. 

The reaction of thin zirconium foils with NF3 in combustion flash lamps 

Relatively strong emission from lead atoms and very weak emission from PbF4 molecules was observed in the reaction of Pb atoms with NF3 in a flow system [6]. 

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In general, the syntheses of these complexes are achieved through (i) nucleophilic addition/substitution reactions of silver(i) fluoride or (ii) transmetallation reactions with other metal alkyl, alkenyl, and aryl complexes. 

The protocol is used for the preparation of 25 kg of the aldehyde in Banyu, and applied to the synthesis of a muscarinic receptor agonist. It is noteworthy that halogen-metal exchange reactions with other metal reagents such as butyllithium or isopropylmagnesium bromide led to more complex mixtures. The Banyu protocol was applicable to similar monoformylation reactions of dibromoheteroarenes (Table 12). 

Of the metals that form luminescent supramolecular entities with gold, that for which most complexes are known is thallium in its +1 oxidation state. As described below, in recent years the contributions of several laboratories have been reported. Nevertheless, in some cases, the papers also report similar reactions with other metals, leading to similar structures. In order to maintain a congruent synthetic description, those examples will be discussed together as they appear in the original work. 

L1 I. ynd Zweitel Synthesis 1974, 658 Matsushita Negishi J. Am. Chem. Sue. 1981, 103, 2882. J. Chem Soc., Chem. Commun. 1982, 160. For similar reactions with other metals, see Larock Bernhardt Driggs J. Organomet. Chem. 1978, IS6, 45 Yoshida Tamao Takahashi-. Kannada Tetrahedron Lett. 1978, 2161 Brown Campbell J. Org. Chem. 1980, 45, 550 Baeckslrom Bjorkling Hdgberg Norin Acta Chem. Scand., Ser. B 1984, 38. 779. 

Reactions with other metal carboxylates are also still occasionally used, as in the following example [16] ... 

Dimerisation Reactions with other Metal-Catalysts... 

Electron transfer reactions with other metal complexes can occur by two mechanisms ... 

DiaUcylcadmium derivatives readily partake in exchange reactions with other metal compounds. NMR studies on the... 

These carbonyl anions are strong nucleophiles (see Nucleophile) and can be used to form a diverse range of new compounds. Protonation gives the /t-hydride (see Bridging Ligand) [(/u.-H) Mo(CO)5 ]. Reactions with other metal carbonyls lead to CO substitution and the formation of metal metal-bonded heteronuclear anions, for example, [Mo(CO)s Fe(CO)4] and [Mo(CO)5-Co(CO)4] . Reaction with main group halides is shown in Scheme 1. The dianion reacts similarly. 

XI. REACTION WITH OTHER METALS AND METAL HALIDES... 

The Barbier reaction with other metals can occupy an entire volume on its own and, hence, will not be reviewed in this work. The interested reader should refer to the references cited at the beginning of this text and those noted in the following for additional information. 

XI. Reaction with Other Metals and Metal Halides 435... 

Reactions with other metal alkoxides and chlorides. 

The nitrosation mechanism of aliphatic amines by metal nitrosyl complexes was studied with various secondary amines and one primary amine (ethylamine) using pentacyanonitrosylferrate (sodium nitroprusside). Very little mechanistic information is available for reactions with other metal nitrosyl complexes (see also Sects. 2.3, 4.3, and 7.2). 

A second question relates to mechanisms of biological interconversions of metallobleomycins. Blm and its Fe-, Cu-, and Zn-complexes are similarly cytotoxic to cells exposed under conditions that minimize extracellular cross reaction with other metal ions, implying that each can be converted into FeBlm. Yet, Cu binds to Blm with higher afifinity than does Fe, and cellular Zn may well be available for reaction with Blm. CuBlm has also been detected in urine after administration of Blm. Opposite conclusions have been reached on whether copper can be removed from Blm by reductive ligand substitution using thiol reagents. 

In reactions with other metal complexes, vanadium(ii) acts as reductant in several ways. There is evidence for both one-electron and two-electron exchange paths in the reaction with mercury(n), activation parameters being measured for both reactions. In the one-electron route, mercury(i)... 

Barbier-Type Reactions with Other Metals... 

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