Bismuthine, bis

Tris[methyl(trimethylsilyl)amino]bismuthine Bi[N(Me)SiMc3]3 is prepared in 54% yield by the reaction of BiBr3 with the corresponding lithium amide in hexane. This compound can be distilled under reduced pressure [66JOM(6) 259]. Similarly, tris[bis(trimethylsilyl)amino]bismuthine Bi[N(SiMe3)2]3 is obtained as a pale yellow powder by treating BiCl3 with lithium hexamethyl-... 

Tetrakis(hexamethyl-phosphoramide-0)phenyl-bismuthine bis(hexafluoro-phosphate)... 

Very small quantities of bismuthine are obtained when a bismuth-magnesium alloy, BijMgj, is dissolved in hydrochloric acid. As would be expected, it is extremely unstable, decomposing at room temperature to bismuth and hydrogen. Alkyl and aryl derivatives, for example trimethylbismuthine, Bi(CHj)3, are more stable. 

The existence of bismuthine was first demonstrated by using a radioactive tracer, Bi (8). Acid treatment of a magnesium plate coated with Bi resulted in the hberation of a volatile radioactive compound. In subsequent experiments, magnesium bismuthide [12048-46-3], Mg Bi, was treated with acid the yield, however, was only one part of bismuthine for every 20,000 parts of bismuth dissolved. Attempts to prepare bismuthine by reduction of bismuth trichloride with a borohydride have not been particularly successful. Experimental quantities ate best prepared by disproportionation of either methylbismuthine [66172-95-0], CH Bi, or dimethylbismuthine [14381-45-4], C2H. Bi (7) ... 

CgH BiBr2, and diphenylbromobismuthine [39248-62-9] C22H2QBiBr, respectively, with lithium aluminum hydride or sodium borohydride at low temperatures yielded only black polymeric substances of empirical formula C H Bi (33). It has been claimed (34) that dimethylbismuthine and diphenylbismuthine can be used as cocatalysts for the polymerisation of ethylene (qv), propylene (qv), and 1,3-butadiene. The source of these bismuthines, however, was not mentioned. 

All three carboa—bismuth boads of trihen zylhismuthine [99715-52-3], C2 H2 Bi, (64) and triphenylbismuthine (65) can be cleaved by alkafl metals. Under some conditions, however, tertiary bismuthines react with sodium or potassium to yield secondary bismuthides. Thus a number of sodium dialkylbismuthides have been obtained by the iateraction of a trialkylbismuthine and sodium ia Hquid ammonia (66—69) ... 

In 1996, we started more detailed investigations on group 13/15 compounds containing the heavier elements of group 15, Sb and Bi, focussing on the synthesis of aluminum and gallium stibines and bismuthines. At the same time. Wells et al. also began to prepare M—Sb adducts and heterocycles (M = B, Ga, In). These studies, which are the object of this review, resulted in... 

Reliable information on the thermodynamic stability of group 13/15 adducts is usually obtained by gas phase measurements. However, due to the lability of stibine and bismuthine adducts in the gas phase toward dissociation, temperature-dependent H-NMR studies are also useful for the determination of their dissociation enthalpies in solution [41b], We focussed on analogously substituted adducts t-BusAl—E(f-Pr)3 (E = P 9, As 10, Sb 11, Bi 12) since they have been fully characterized by single crystal X-ray diffraction, allowing comparisons of their thermodynamic stability in solution with structural trends as found in their solid state structures. 

Additional studies on R3AI—Bi(Tms)3 (R = Me 13, Et 14) showed the extreme lability of alane-bismuthine adducts toward dissociation in solution. Their H-NMR spectra at ambient temperature only show one resonance due to the Al—R groups, while at -70 °C two resonances of the A1—R groups in a... 

To date, 15 stibine R3M Sb(R/)3 (M = B, Al, Ga, In) and six bismuthine adducts R3M Bi(R )3 (M = Al, Ga) have been structurally characterized by single crystal X-ray diffraction. Their M-E, M-X and E-X bond lengths as well as X-M-X and X-E-X bond angles are summarized in Tables VI, YII and VIII. Figures 6-9 show the solid state structures of four representative adducts. 

It should also be stated that the M-E bond distances within the Et3M <— E(SiMe3)3 and t-Bu3M <- E(/-Pr)3 adduct families increase by about 40 pm according to the increase of the covalent radii of the group 15 element (rCOv(P) 110 pm, rcov(Bi) 150 pm). Within the sterically overcrowded t-Bu3M <— E(z-Pr)3 adduct families the arsine and bismuthine adducts show... 

The tricobalt-bismuthine complex [Bi Co(CO)4 3], 136, has been described by Schmid (133) and can be synthesised by two routes involving either the reaction between BiCl3 and [Co(CO)4] or between bismuth metal and... 

Methyl bis(l-naphthyl)bismuthinate, Np.BiOCH,. The reagent is obtained in 80% yield by reaction of tris(l-naphthyl)bismuthine, Np3Bi, with chloramine-T in methanol. ... 

Dimethylbismuthano phenyl tellurium decomposes at room temperature to trimethyl-bismuthine and methylbismuthinidene bis phenyl telluriuml1. 

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