Nitrogen-bismuth compounds

The bismuth-nitrogen bonds in these compounds are labile and decomposition slowly occurs at room temperature they may be stored at —78°C. Some reactions are shown in Scheme 7. 

A solution of potassium iodide and bismuth subnitrate in acetic acid, used for tiie detection of all loids and quaternary nitrogen compounds. 

The phosphoms azides P(N3)3, P(N3)4+, P(N3)5, and P(N3)6 have long been known (see Phosphorus-Nitrogen Compounds). More recently, the binary arsenic, antimony, and bismuth M(N3)3, the cations As(N3)4+ and Sb(N3)4+, and the arsenic and antimony M(N3)4 and M(N3)e anions have been synthesized. While the cations and binary azides are very sensitive(the bismuth compound has not been isolated), the anions, in combination with sufficiently large cations such as As(Ph)4+, are less sensitive. Attempts to prepare the As(V) and Sb(V) pentaazides resulted in explosions. 

Reactions of organoantimony and -bismuth dihalides with various nitrogen nucleophiles give the corresponding nitrogen compounds. Several examples are shown in equations 245 246 247 = and 248 . ... 

The organotin derivatives of phosphorus, arsenic, antimony, and bismuth have much in common with the corresponding derivatives of nitrogen, the most obvious difference being that the nitrogen compounds are unreactive towards oxygen, whereas the others are oxidised in air ... 

CC95], and oxidation of organosulfur and nitrogen compounds with bismuth nitrate (Scheme 5.17) [96CC1847, 97CL1229]. 

This article is concerned mainly with the simple halides of phosphorus, arsenic, antimony, and bismuth compounds that also contain other elements or groups will be considered only to a limited extent. Nitrogen compounds show special features associated with the absence in nitrogen of d electrons for bonding, and are not easily discussed together with compounds of the heavier elements they will therefore be omitted. Bismuth has metallic properties that differentiate its compounds from those of elements in the middle of the group the break in properties between the compounds of antimony and bismuth is not, however, so marked as that between compounds of nitrogen and phosphorus. 

There are a large number of compounds which contain bismuth-nitrogen bonds, but very few in which such bonding represents the main framework of the bonding. There does exist BiCls coordination compounds such as the stable colourless [BiCl3(NH3)3] or the unstable red [(BiCl3)2(NH3)]. These compounds are described in more appropriate sections, except where a point about the Bi—bond is being made. 

Few organobismuth-nitrogen compounds have been structurally characterized. The azide Me2BiN3 forms supramolecular chain-like arrays, similar to those described for arsenic and antimony. Again, the bridging bonds are equalized (Bi-N 2.49 and 2.50 A). The chains are bent at nitrogen (Bi-N-Bi 123°) and almost linear at bismuth (N-Bi-N 169°) [476]. 

Halogenide complexes of heavy metals such as mercury bismuth, cadmium and antimony can be used in the titration of some basic heterocyclic nitrogen compounds < and among others, thiamineS > In this latter example, thiamine was titrated... 

Smith JD (1973) The chemistry of arsenic, antimony and bismuth. Pergamon, Oxford Allcock HR (1972) Phosphorus-nitrogen compounds. Academic, New York Hahnann M (ed) (1972) Analytical chemistry of phosphorus compounds. WUey, New York... 

Pentaphenylbismuth is a violet-colored, crystalline compound that decomposes spontaneously after standing for several days in a dry nitrogen atmosphere. With a variety of agents, eg, hydrohahc acids, halogens, and triphenylboron, one phenyl group is cleaved to form quaternary bismuth compounds. 

Supplementary Work, Vol 24 Perfluorohnloorganic Compounds of Mam Group Elements Part 3 Phosphorus, Arsenic, Antirnon and Bismuth Compounds Perfhiorohaloorganic Compounds of Main Group Elements Part 5 Compounds oj Nitrogen (Heteroc clrc Compounds)... 

The effect of a particular element on the odour of its compound seems also to lend support to the residual affinity theory, for it is only the elements which possess residual affinity in certain of their compounds, which function as osmophores. Oxygen, nitrogen, sulphur, phosphorous, halogens, arsenic, antimony, bismuth, etc., whose valencies vary under certain conditions are powerfully osmophoric whereas carbon, hydrogen, and many others which have a constant valency are practically non-osmophoric, and it is very instructive to note that the element is osmophoric when it is not employing its full number of valencies and therefore has free affinity. 

Metals may also be linked through an oxygen or nitrogen atom to form a stable metal complex without a carbon-metal bond. These include metal complexes of ethylenediamine tetraacetate (EDTA), diethylenetriamine pentaacetate (DTPA), or ethylenediamine tetramethylphosphonate (EDTMP). Metalloid compounds include antimonyl gluconate and bismuth salicylate. 

The Dragendorjf reagent is available in different compositions, and it mainly stains nitrogen-containing compounds, producing colored zones on a white background. For solntion a 1.7 g of basic bismuth nitrate and 20 g of tartaric acid are dissolved in 80 ml of water. For solution b 16 g of potassium iodide are dissolved in 40 ml of water. The final spray reagent is mixed from solution a and b in the... 

One of the simplest examples for such effects is the oxidation of ammonia with iron oxide-bismuth oxide as a catalyst. Here, the addition of bismuth oxide results in the formation of nitrous oxides as the main product whereas an iron oxide catalyst without bismuth oxide yields nitrogen almost exlcusively. Selectively guiding catalysts become increasingly important in the synthesis of organic compounds, e.g., in the hydrogenation of carbon monoxide where the type of obtainable product can be varied, within wide limits, by the kinds of catalysts and promoters which are employed. 

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