Bismuth bonding

Treatmeat of 1-phenyl-2,5-dimethylhism ole [88635-81-8], with sodium ia Hquid ammonia results in cleavage of the phenyl—bismuth bond and... 

Dibismuthines are very sensitive to oxidation. Thus tetramethyldibismuthine fumes ia air, and tetraphenyldibismuthine ia toluene solution rapidly absorbs oxygen. Under controlled conditions, dibismuthines react with chalcogens resulting ia cleavage of the bismuth—bismuth bond and iasertion of a chalcogen atom (105,138,140—142) ... 

See Table XII and Chart 5.) The stability of the thiolate-bismuth bond has allowed for the assessment of interactions between bismuth... 

Although it was first prepared by Verma et al. in 1983 starting from Bi(III) trifluoroacetate [58], our group developed another strategy for the preparation of Bi(OTf)3 [32]. The key point of our synthetic strategy is based on the acidic cleavage of the three carbon-bismuth bonds of triphenylbismuth by triflic acid in dichloromethane (Scheme 1). A study of the hydration of Bi(0Tf)3xH20 revealed that this compound can exist as three different hydrates, the nonahydrate, the tetrahydrate, and the dehydrate [35], The structures of the nona- and tetrahydrate forms have been determined by ab-initio calculations [35] and XRD [36]. 

Antimony and bismuth bonds to arsenic are dealt with in Sections 28.10.2 and 28.16.2 under antimony and bismuth, respectively. 

The silicon-bismuth bond has been demonstrated in a number of compounds such as Bi(SiF3)3, a volatile crystalline compound184 which decomposes on heating it is air and moisture sensitive. Germanium-bismuth compounds can be prepared by the use of Bi(SiEt3)3 (equations 52 and 53).185... 

Selenium-bismuth bonds are formed in the mutual cleavages of dibismuthines and diselenides (equation 69).218 This particular compound is stable at -30 °C, unlike the tellurium analogue. At room temperature the compound disproportionates to give the diseleno derivative (equation 70). Similar behaviour was noted in the analogous sulfur compounds (Section 28.17.2.1). 

All three carbon—bismuth bonds of tribenzylbismuthine [99715-52-3], C21H21Bi, (64) and triphenylbismuthine (65) can be cleaved by alkali 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 interaction of a trialkylhismnthine and sodium in liquid ammonia (66—69) ... 

We have essentially exhausted all of the directly measured enthalpies of formation of compounds containing carbon-arsenic, -antimony and -bismuth bonds. However, let us now make use of other thermochemical data and see what can be derived using some plausible estimates. And barring that, let us see what new enthalpies of formation would become available if only some new measurement were made. 

Only a few compounds containing six carbon-antimony or -bismuth bonds are known. The first compound of this type was obtained as colorless crystals by Wittig and Clauss from PhjSb and PhLi (equation 177 ). The ate complex 66 reacts with water forming PhsSb. 

G. Preparation of Organoarsenic(lll) Compounds Containing Arsenic-Phosphorus, -Antimony or -Bismuth Bonds... 

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