Trialkyl arsines

Many carbon compounds, e.g. hydrocarbons, ketones, organic acids, bases and esters, dissolve in arsenic trichloride with formation of additive or complex compounds. The organic derivatives of arsenic are described in Volume XI, Part II, of this Series. Trialkyl arsines are formed by the addition of alkali to the double salts obtained by the interaction of zinc dialkyls and arsenic trichloride—... 

Trialkylarsine Sulphides.— Direct addition of sulphur and trialkyl-arsine takes place in the case of the ethyl compound, the product also resulting from the interaction of diethylarsine and carbon disulpMde at 120 C., or on heating ethylarsine disulphide at 195° C. Tri-methylarsine sulphide is obtained from dimethylarsine and liquid... 

The pure trialkyl arsines and stibines are removed from the equilibrium mixtures by distillation at very low pressure (240). 

Trialkyl-arsines and -stibines, and triarylarsines, add alkyl iodides, yielding quaternary arsonium and stibonium iodides, R4MI or R3R MI. 

Trialkyl arsine sulphides -480 -20.83 vs As-S str, band position dependent on size of alkyl... 

In their study comparing reduced and atmospheric pressure MIP detection, Olsen et al. found for the latter system a one pg detection limit for mercury, with selectivity over carbon of 10,000 dilalq l mercurials, diarylmercurials, monoalkyl mercury chlorides, trialkyl arsines and triarylarsines were all chromatographed [36]. GC-MIP of volatile... 

Trialkyl- and triarylarsine sulfides have been prepared by several different methods. The reaction of sulfur with a tertiary arsine, with or without a solvent, gives the sulfides in almost quantitative yields. Another method involves the reaction of hydrogen sulfide with a tertiary arsine oxide, hydroxyhahde, or dihaloarsorane. X-ray diffraction studies of triphenylarsine sulfide [3937-40-4], C gH AsS, show the arsenic to be tetrahedral the arsenic—sulfur bond is a tme double bond (137). Triphenylarsine sulfide and trimethylarsine sulfide [38859-90-4], C H AsS, form a number of coordination compounds with salts of transition elements (138,139). Both trialkyl- and triarylarsine selenides have been reported. The trialkyl compounds have been prepared by refluxing trialkylarsines with selenium powder (140). The preparation of triphenylarsine selenide [65374-39-2], C gH AsSe, from dichlorotriphenylarsorane and hydrogen selenide has been reported (141), but other workers could not dupHcate this work (140). 

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. 

Besides the thiocyanates, just mentioned, other 5-donor complexes which are of interest are the dialkyl sulfides, [MCl3(SR2)3], produced by the action of SR2 on ethanolic RhCl3 or on [IrClg] ". Phosphorus and arsenic compounds are obtained in similar fashion, and the best known are the yellow to orange complexes, [ML3X3], (M = Rh, Ir X = Cl, Br, I L = trialkyl or triaryl phosphine or arsine). These compounds may exist as either mer or fac isomers, and these are normally distinguished by their proton nmr spectra (a distinction previously made by the measurement of dipole moments). An especially... 

Silver iodide derivatives of trialkyl-phosphines and -arsines were prepared in 1937 for comparison with their copper(I) iodide analogues.201 The preparations involved shaking the ligands with silver iodide dissolved in concentrated aqueous KI. The products were found to be tetramers and of similar structure to the Cu1 complexes. The Pr As silver complex was isomorphous with [Cul-AsEt3]4. Molecular weight determinations in a range of organic solvents showed that partial dissociation occurred in solution. 

The response of films containing polyester plasticizers or the trialkyl phosphate to the arsine-epoxy adduct was noteworthy and, to the degree obtained, unexpected. 

Trialkyl- and triarylphosphines, -arsines, and -stibines, and chelating di- and triphosphines and -arsines are widely used as jr-acid ligands (Section 10-17). 

Osmium pentacarbonyl is a convenient precursor to other osmium carbonyl complexes. Hydrogenation gives the dihydride OsH2(CO)4. This hydride is not acidic with a p/fa of 18.5 but it can be deprotonated by strong bases to give [OsH(CO)4] and reduced by sodium (Scheme 23). Substitution of CO on Os(CO)5 by trialkyl or triarylphosphines, arsines, or stibenes gives Os(CO)4L or Os(CO)3L2. Other carbonyl phosphine complexes result from the reduction of osmium halides by alcohols in the presence of the tertiary phosphine. 

Ignition or explosive reaction with metals (e.g., aluminum, antimony powder, bismuth powder, brass, calcium powder, copper, germanium, iron, manganese, potassium, tin, vanadium powder). Reaction with some metals requires moist CI2 or heat. Ignites with diethyl zinc (on contact), polyisobutylene (at 130°), metal acetylides, metal carbides, metal hydrides (e.g., potassium hydride, sodium hydride, copper hydride), metal phosphides (e.g., copper(II) phosphide), methane + oxygen, hydrazine, hydroxylamine, calcium nitride, nonmetals (e.g., boron, active carbon, silicon, phosphoms), nonmetal hydrides (e.g., arsine, phosphine, silane), steel (above 200° or as low as 50° when impurities are present), sulfides (e.g., arsenic disulfide, boron trisulfide, mercuric sulfide), trialkyl boranes. 

Trialkyl and triphenyl substituted tertiary arsines and stibines are, like the phosphine analogues, suitable as ligands in transition metal complexes in several oxidation states, due to their low reduction potentials (cf Table 7 in Section III.A.l) and relatively high oxidation potentials (cf Table 14 in Section V.A). 

Hibbert now decided to study abroad for his doctorate, and he arrived at the University of Leipzig in October, 1904, to work under Professor Arthur Hantzsch on addition products of trialkyl derivatives of arsines, phosphines, and stibines. Hibbert published an article on the preparation of the trialkyl derivatives (by means of the Grignard reaction) in Berichte for 1906, and, in the following year, he and Hantzsch described the addition products in the same Journal. In 1906, Hibbert was awarded the Ph. D. degree mmma cum laude by the University of Leipzig. During his two years... 

With trialkyl phosphines and arsines cuprous and argentous halides form the tetrameric molecules [R3P(As). Cu(Ag)X] 4, but Au forms only R3P(As). AuX. In addition to the cases already noted, X-ray studies have demonstrated the formation of two collinear bonds by Au(i) in Aul, which consists of chains of the type... 

The reaction of dialkyl(aryl) phosphines and arsines with trialkyl alanes is analogous to that for the corresponding nitrogen compounds. After splitting off 1 mole of alkane (with phosphines at ca. 140°-160°C with... 

Trialkyl- and triaryl-phosphines, -arsines and -stibines are all good donors toward rf-group transition metals and chelating di- and tri-phosphines and -arsines have been especially widely used as 7r-acid ligands (Section 22-13). The oxides, R3MO, also form many complexes, but they function simply as donors. Trialkyl- and triaryl-phosphines, -arsines and -stibines generally react with alkyl and aryl halides to form quaternary salts ... 

Condensation of arsenic trihalides with alkyl or aryl halides in the presence of metallic sodium, analogous to a Wurtz-Fittig reaction, leads to trialkyl- and triaryl-arsines. E.g., tribenzylarsine is obtained by prolonged boiling of benzyl chloride and arsenic trichloride in ether containing sodium and a little ethyl acetate 501 tripropylarsine is obtained similarly from propyl chloride, arsenic... 

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