Monohalides
Group 65 includes well-known sulphenyl (Y = S) and selenenyl (Y = Se) halides, typically obtained through the halogenolysis of disulphides or diselenides Many aromatic derivatives within this group are stable and serve as crucial reagents in modern synthetic chemistry Surprisingly, until recently, 2-naphthalenetellurenyl iodide was the only well-characterized tellurenyl halide, despite the stability of other organic compounds with Te-halogen bonds In 1975, additional unstable aromatic analogues were synthesized, which react with halide ions to form species like RTeBrCl- (isolated as tetraphenylarsonium salts) X-ray studies indicate a T-shaped geometry with a nearly linear X-Te-X' arrangement in these ions, while S and Se do not form similar compounds.
Diorganyl chalcogenides, represented as R,Y, react with halogens to form compounds that exhibit varying stability, increasing from sulfur (S) to tellurium (Te) and from iodine (I) to fluorine (F) The least stable species, such as R,SI, behave like charge-transfer complexes, while bromides and iodides tend to dissociate upon heating or dissolution In non-aqueous solutions, dissociation is not observed, but aqueous solutions show conductivity due to the presence of aqua ions, RYX(H2O)+, and hydrolysis products, R,YX(OH) Diorganyltellurium dihalides are stable, crystalline compounds with a trigonal bipyramidal geometry, often used as intermediates in the synthesis of pure tellurides Fluorides can be synthesized through metathesis with AgF or NaF, or by direct fluorination at low temperatures, although similar compounds with selenium (Se) and tellurium (Te) have not been reported.
Organyl chalcogen trihalides represent a significant and extensively researched category of compounds These compounds can be synthesized through the halogenation of diselenides or ditellurides, or by employing electrophilic substitution in activated aromatic nuclei using selenium and tellurium tetrachloride The stability of these compounds varies, generally ranging from fair to good, with the highest stability observed in certain types.
The trihalides of tellurium (Te) exhibit tetravalency and play a significant role in synthesizing various products Upon hydrolysis, trihalides with sulfur or selenium (X = S, Se) yield sulphinic or seleninic acids, while their tellurium counterpart produces a formal tellurinyl chloride, RTe(0)Cl, which behaves similarly to inorganic oxide chlorides The structure of PhTeCl is polymeric, featuring bridging chlorine atoms that surround each tellurium atom with four chlorine atoms In contrast, 8-ethoxy-4-cyclooctenyltellurium trichloride is established as a monomer due to the presence of a bulky organic radical that shields the TeCl group.
Halogen compounds of sulfur (S) and selenium (Se) exhibit notable similarities in their properties and reactivities, while tellurium (Te) shows a more metallic character, leading to distinct behavior in its organic derivatives.
XI CHALCOGEN DERIVATIVES OF GROUP V ELEMENTS
Sulphenamides represent a well-studied class of compounds, while selenenyl amides, or selenenamides, are less common and have been primarily synthesized through reactions involving selenenyl halides or alkoxides with ammonia or amines Current evidence suggests that selenenamides may be less stable than their sulphenamide counterparts, although this view may change as more compounds in this category are discovered.
RYNH, RN =Se=NR R,PY
Trifluromethylselenyl bromide reacts with ammonia to produce various distillable liquids, including CF3SeNH2 and (CF3Se)2Nn7, which behave similarly to conventional amines Notably, CF3SeNH2 can react with isocyanates to form CF3Se-substituted ureas Additionally, there appears to be no existing reports on tellurenamides (69; Y = Te).
The selenenyl amides react with nucleophiles in the same way as selenenyl halides Thus,
N-phenylselenenylphthalimide, prepared from potassium phthalimide and phenylsele- nenyl ~ h l o r i d e ~ * , ~ ~ , is a useful substitute for selenenyl halides in a great variety of reactions (cf the reactions of similar N-sulphenylphthalimide~~~)
Recent studies have identified stable chalcogen-nitrogen compounds, including N-4-methylbenzenesulphonylated selenimides and tellurimides, which have been analyzed using spectroscopy and X-ray diffraction techniques Additionally, known selenoximides serve as stable analogues to the extensively researched sulfoximides.
The easily prepared selenium diimides (70; R = t-Bu, 4-MeC6H4S02) have been utilized as efficient reagents for allylic amination of alkenesg4
Tertiary phosphines react with elemental S or Se to form phosphine sulphides (71;
Y = S) and phosphine selenides (71; Y = Se) Tertiary arsines and stibines form similar compounds More recently, elemental Te has been found to react similarly to give phosphine tellurides (71; Y = Te)95
Diphosphanes react with ditellurides to produce telluradiphosphanes (R,PTePR) through the insertion of tellurium extracted from the ditelluride In contrast, the corresponding reaction in the selenium series leads to the formation of a substituted three-membered ring compound, which is derived from selenadiphosphirane.
Phosphorus trichloride and arsenic trichloride react with (CF,Se),Hg to form the substituted phosphines and arsines, (CF,Se),P and (CF,Se),AsS7
Many derivatives of selenium isologues of phosphorus acids have been identified, while only a limited number of analogous tellurium compounds have been studied due to their high sensitivity to air Historically, it was demonstrated that an alkaline solution of dialkyl phosphite can react effectively with sulfur, selenium, or tellurium to produce chalcogenophosphates.
~ogenate)~' The Te compound (EtO),P(O)TeNa has recently been utilized as an eficient reagent for the deoxygenation of epoxidesg9
1 Organic derivatives of S, Se and Te-an overview
Thiophene (72) represents the classical sulphur analogue of benzene By the same token, selenophene (73) and tellurophene (74) assume similar key compound roles in the heterocyclic chalcogen chemistry
Selenophene derivatives have been recognized for nearly a century, with the parent compound first synthesized from acetylene and selenium in 1927 Comprehensive research into its properties and chemistry has consistently demonstrated its remarkable resemblance to thiophene.
Tellurophenes are less well explored, and tellurophene (74) itself remained unknown until 1972 when its rather straightforward synthesis disproved the suspected instability of
Compound 74 exhibits properties that closely resemble those of compounds 72 and 73, with the key distinction being that 74 generates a stable 1,1-dichloro compound (75) when reacted with Cl2, unlike 72 and 73 This similarity extends to various other tellurium-containing heterocyclic systems.
Recent research has focused on heterocyclic selenium compounds, which are similar to sulfur-containing 1,2-dithioles and 1,3-dithioles, as well as related systems like tri-thiapentalene and tetrathiafulvalene These studies are particularly relevant to the exploration of organic materials exhibiting metallic conductivity An example of this is tetramethyl tetraselenafulvalene (TMTSF), which forms a charge-transfer complex with 2,5-dimethyl-7,7,8,8-tetracyano-p-quinodimethane.
Recent studies have revealed that certain salts, specifically TMTSF2X, where X denotes various inorganic anions, demonstrate superconductivity that is significantly higher than that of related sulfur compounds, surpassing it by a factor of ten Additionally, the synthesis of a corresponding tellurium compound has recently been reported, marking a notable advancement in the field of superconductivity research.
Saturated tellurium heterocycles, including l,Coxatellurane and l,Cselenatellurane, show notable similarities to their selenium counterparts, which include well-known nitrogen heterocycles like selenazoles and selenadiazoles However, analogous tellurium compounds are surprisingly scarce An example is benzo[4-1,2-tellurazole], which displays unusual physical properties due to its very short intermolecular interactions.
Te-N bondslo5 To what extent the shortage of such compounds is caused by their properties or rather by the lack of appropriate synthetic methods remains to be established
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Edited by S Patai and Z Rappoport
General and theoretical aspects of organic compounds containing selenium or tellurium
Department of Chemistry, Memorial University of Newfoundland, St John's, Newfound- land, AIB 3x7, Canada
Department o f Chemistry, University of Toronto, Toronto, M5S l A l , Canada
Even before Mendeleev introduced the concept of periodicity of the chemical elements, certain atoms and their compounds were studied in relation to one another One of these
(eV) of Group VI elements and their dihydrides A comparison of experimental first ionization potentials