Bonds bismuth-sulfur

The favorable bismuth-sulfur bond translates into thermal and hydrolytic stability for the thiolates of bismuth, which are currently more numerous than the alkoxide derivatives (Table II). Various monomeric trithiolates have been identified, and most adopt predictable structural formulas, although the solid-state structures reveal interesting intermolecular and intramolecular interactions. 

Table 25 Bismuth-Sulfur Bond Lengths and Angles...

Dalzin (bis(allylthiocarbamido)hydrazine) forms sparingly soluble complexes (29) in which it is bonded through sulfur and nitrogen atoms (Section 10.2.7) but the bright orange-red bismuth complex can be extracted into chloroform for a spectrophotometric determination provided cyanide is present to mask copper. 1,4-Diphenylthiosemicarbazide PhNHNC(SH)NHPh can be used for the spectrophotometric determination of ruthenium after extraction of its violet-red complex into chloroform. 

This type of association is better demonstrated in organobismuth chemistry. Thus, the molecules of diphenylbismuth(III) isopropylxanthate, Ph2BiS2COPr, are self-organized in helical chains, 198, with distinct primary (Bi-S 2.66 A) and secondary (intermolecular Bi- -S 3.23 A) bismuth-sulfur bonds [467]. 

The ylides have been classified on the basis of the heteroalom covalently bonded to the carbanion. Accordingly, they can be differentiated into nitrogen ylide (Scheme 2), sulfur ylide Scheme 3, phosphorus ylide Scheme 4, arsenic ylide Scheme 5, antimony ylide (Scheme 6), bismuth ylide (Scheme 7) and thallium ylide (Scheme 8). 

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). 

The X-ray crystallographic study of compound 1 has shown that the bismuth center is described best as a distorted pentagonal bipyramidal. The Bi-S bond lengths are 2.581(4), 2.627(5) and 2.731(3) A, and the Bi-O bond lengths are 2.536(9), 2.575(11) and 2.650(9) A. In addition, there is some intermolecular interaction between the bismuth and sulfur atoms (3.494(5) and 3.551(5) A), which causes a dimeric structure in the solid state [92POL1219]. 

The X-ray structure analysis of compound 2 has shown that the bismuth center is surrounded by six sulfur atoms to form a trigonal antiprismatic geometry. All three dithiocarboxylate ligands are non-equivalent and the Bi-S bonds can be divided into two types short (2.617(2), 2.626(1) and 2.647(1) A) and long (2.963(2), 3.040(1) and 3.108(2) A). One of the sulfur atom coordinates weakly to the neighboring bismuth center (3.689 A) to form a dimeric structure in the solid state [87IC1453]. 

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