Stibines

Volatile hydrides, except those of Periodic Group VII and of oxygen and nitrogen, are named by citing the root name of the element (penultimate consonant and Latin affixes. Sec. 3.1.2.2) followed by the suffix -ane. Exceptions are water, ammonia, hydrazine, phosphine, arsine, stibine, and bismuthine. 

Stannic and stannous, see under Tin Stibine, see Antimony hydride Stibnite, see Antimony(III) sulflde Stolzite, see Lead tungstate(VI)(2—)... 

Ozone ALkenes, aromatic compounds, bromine, diethyl ether, ethylene, HBr, HI, nitric oxide, nitrogen dioxide, rubber, stibine... 

Lead—antimony or lead—arsenic ahoys must not be mixed with lead—calcium (aluminum) ahoys in the molten state. Addition of lead—calcium—aluminum ahoys to lead—antimony ahoys results in reaction of calcium or aluminum with the antimony and arsenic to form arsenides and antimonides. The dross containing the arsenides and antimonides floats to the surface of the molten lead ahoy and may generate poisonous arsine or stibine if it becomes wet. Care must be taken to prevent mixing of calcium and antimony ahoys and to ensure proper handling of drosses. 

Copper sulfate, in small amounts, activates the zinc dust by forming zinc—copper couples. Arsenic(III) and antimony(TTT) oxides are used to remove cobalt and nickel they activate the zinc and form intermetaUic compounds such as CoAs (49). Antimony is less toxic than arsenic and its hydride, stibine, is less stable than arsine and does not form as readily. Hydrogen, formed in the purification tanks, may give these hydrides and venting and surveillance is mandatory. The reverse antimony procedure gives a good separation of cadmium and cobalt. 

Semiconductor and Solar Cells. High purity (up to 99.9%) antimony has a limited but important appHcation in the manufacture of semiconductor devices (see Semiconductors). It may be obtained by reduction of a chemically purified antimony compound with a high purity gaseous or soHd reductant, or by thermal decomposition of stibine. The reduced metal may be further purified by pyrometaHurgical and zone melting techniques. 

Phenylstibine [58266-50-5] C H Sb, has been obtained by the reduction of phenyldiio do stihine [68972-61-2] CgH3l2Sb, (73) or phenyldichlorostibine [5035-52-9] 031130.2, (74) with lithium borohydride. It has also been prepared by the hydrolysis or methanolysis of phenylbis(trimethylsilyl)stibine [82363-95-9] C22H23Si2Sb (75). Diphenylstibine [5865-81-6] C22H22Sb, can be prepared by the interaction of diphenylchlorostibine [2629-47-2] C22H2QClSb, with either Hthium borohydride (76) or lithium aluminum hydride (77). It is also formed by hydrolysis or methanolysis of diphenyl (trimethylsilyl)stibine [69561-88-2] C H SbSi (75). Dimesitylstibine [121810-02-4] h.3.s been obtained by the protonation of lithium dimesityl stibide with trimethyl ammonium chloride (78). The x-ray crystal stmcture of this secondary stibine has also been reported. 

The aromatic primary and secondary stibines are readily oxidized by air, but they are considerably more stable than their aHphatic counterparts. Diphenylstibine is a powerful reducing agent, reacting with many acids to Hberate hydrogen (79). It has also been used for the selective reduction of aldehydes and ketones to the corresponding alcohols (80). At low temperatures, diphenylstibine undergoes an addition reaction with ketene (81) ... 

Another exceUent method for preparing tertiary stibines involves the interaction of an organostibide and an alkyl or aryl haHde (91,92). This method is of particular value in preparing un symmetrical tertiary stibines. For example, an interesting hybrid ligand has been obtained by the foUowing reaction carried out in Hquid ammonia (93) ... 

Tri alkylstibines are sensitive to oxygen, and in some cases they ignite spontaneously in air. Trimethyl stibine [594-10-5] C3H2Sb, may explode on... 

Tertiary stibines have been widely employed as ligands in a variety of transition metal complexes (99), and they appear to have numerous uses in synthetic organic chemistry (66), eg, for the olefination of carbonyl compounds (100). They have also been used for the formation of semiconductors by the metal—organic chemical vapor deposition process (101), as catalysts or cocatalysts for a number of polymerization reactions (102), as ingredients of light-sensitive substances (103), and for many other industrial purposes. 

Polymeric substances, (RSb) or (ArSb), have been obtained by the decomposition of primary stibines (67,74), the reaction of primary stibines with hydrogen chloride (68), the treatment of primary stibines with diben2yhnercury (137), or the reduction of dibalostibines (138—140). Most of these polymers have not been well characteri2ed. 

Stibonic and Stibinic Acids. The stibonic acids, RSbO(OH)2, and stibinic acids, R2SbO(OH), are quite different in stmcture from their phosphoms and arsenic analogues. The stibonic and stibinic acids are polymeric compounds of unknown stmcture and are very weak acids. lUPAC classifies them as oxide hydroxides rather than as acids. Thus CgH3SbO(OH)2 is named phenyl antimony dihydroxide oxide [535-46-6], the Chemical Abstracts n.2ixn.e is dihydroxyphenylstibine oxide [535-46-6], CgH OgSb. 

Dimethyl stibinic acid [35952-95-5], C2H202Sb, diethylstibinic acid [35952-96-6], C4H 02Sb, dipropylstibinic acid [35952-97-7], CgH 302Sb, and dibutylstibinic acid [35952-98-8], CgH2202Sb, have been prepared in this manner. Except for the dimethyl compound, they can be readily recrystaUi2ed from organic solvents. 

Stibine Oxides and Related Compounds. Both aUphatic and aromatic stibine oxides, R SbO, or their hydrates, R3Sb(OH)2, are known. Thus both dihydroxotrimethylantimony [19727-41-4], C3H2202Sb, and trimethyl stibine oxide [19727-40-3], C H OSb, have been prepared. The former maybe readily obtained by passing an aqueous solution of dichi orotrimethyl antimony [13059-67-1], C3H2Cl2 > through an anionic-exchange resin (151). 

C. A. McAuliffe and W. Levason, Studies in Inorganic Chemistry, Vol. 1, Phosphine, Arsine and Stibine Complexes of the Transition Elements, Elsevier, Amsterdam, The Netherlands, 1979. 

Although trialkyl- and triarylbismuthines are much weaker donors than the corresponding phosphoms, arsenic, and antimony compounds, they have nevertheless been employed to a considerable extent as ligands in transition metal complexes. The metals coordinated to the bismuth in these complexes include chromium (72—77), cobalt (78,79), iridium (80), iron (77,81,82), manganese (83,84), molybdenum (72,75—77,85—89), nickel (75,79,90,91), niobium (92), rhodium (93,94), silver (95—97), tungsten (72,75—77,87,89), uranium (98), and vanadium (99). The coordination compounds formed from tertiary bismuthines are less stable than those formed from tertiary phosphines, arsines, or stibines. 

Complexes with absorbing solution Arsine, stibine, hydrogen sulfide... 

In volume terms the most important class of fire retardants are the phosphates. Tritolyl phosphate and trixylyl phosphate are widely used plasticisers which more or less maintain the fire-retarding characteristics of PVC (unlike the phthalates, which reduce the flame resistance of PVC products). Better results are, however, sometimes obtained using halophosphates such as tri(chloroethyl) phosphate, particularly when used in conjunction with antimony oxide, triphenyl stibine or antimony oxychloride. 

Some materials, such as arsine, phosphine, toluene di-isocyanate and stibine, may be present in concentrations in excess of their hygiene standards yet undetectable by smell. 

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