Bismuth trihalides complexes

The preparation of 1 1 complexes of arsenic, antimony, and bismuth trihalides with dithio-oxamides has been reported.647 I.r. spectra of the arsenic compounds point strongly to the probability of dimeric, octahedral structures, but with the two heavier Group V elements square-pyramidal structures have been suggested. Crystalline adducts 2MBr3,3dioxan, where... 

Treatment of a bismuth trihalide with electron-rich arenes affords arene-BiX3 TT-complexes. When the reaction is carried out in the presence of AICI3, the corresponding cationic ir-complexes are formed [87AG(E)74]. The arenes employed so far are benzene, toluene, mesitylene, hexamethyl-benzene, perylene, pyrene, acenaphthene, phenanthrene, fluorene, and fluor-anthene-p-xylene (1/0.5). The isolated compounds are summarized in Table 2.29. 

Photoelectron spectra for the antimony trihalides and Sb, Cl, and Br n.q.r. spectra for a number of adducts of the trichloride and bromide have been reported. The complex SbCl3,GaCl3 has been isolated, whereas a simple eutectic only is observed in the SbCl3-AlCl3 system. Antimony and bismuth halide complexes with substituted l,2-dithiol-3-thiones can be obtained, and the... 

Bismuth trihalides along with the analogous arsenic and antimony compound form complexes with metal carbonyls with bismuth, however, only neutral species such as Cl2BiFe(CO)2Cp and Bi[Co(CO)3PPh3l3 were isolated. 

Mansfeld and coworkers [127] described the synthesis and characterization of the one-to-one complexes of the bismuth trihalides BiXs (X= Cl, Br, I) with the chelating oxygen-coordinating-donor ligand (iso-PrO)2(0)PCH2P(0)(Oiso-Pr)2. The compounds were analyzed by single crystal XRD, IR, thermal analysis, NMR, ESI MS and conductivity measurements. The combination of these techniques gives a frill description of the structures in the solid state and in solution, and provides information about the use of phosphonic ester complexes as precursors for the formation of bismuth phosphonates. 

Other oxyhalides, mostly oxychlorides and oxybromides, result from the controlled hydrolysis of the trihalides, and are of interest for two main reasons. First, they are quite unrelated to the oxyhalides of bismuth. Although both antimony and bismuth form compounds MOX the structures of the antimony compounds are quite different from those of the compounds BiOX, which have been described on p. 408. The more complex oxyhalides of Sb have no analogues among Bi compounds. Second, a feature of the published structures of the antimony oxyhalides is the coordination of Sb by either three or four O atoms. It should perhaps be remarked here that the investigation of the structures of these complex compounds is difficult, and the precise positions of the O atoms are by no means certain. However, it appears that a feature of these compounds is the formation of extended Sb—O systems, generally layers, interleaved with halogen... 

Bismuth oxide halides BiOX are readily formed as insoluble precipitates by the partial hydrolysis of the trihalides (e.g. by dilution of solutions in concentrated aqueous HX). BiOF and BiOI can also be made by heating the corresponding BiX3 in air. BiOI, which itself decomposes above 300°, is brick-red in colour the other 3 BiOX arc white. All have complex layer-lattice slructurcs. When BiOCl or BiOBr arc heated above 600° oxide halides of composition Bi2403l Xio arc formed, i.e. replacement of 5 O atoms by 10 X in Bi240j6. (Bi203>. 

---