Sulfur ligands bismuth

An X-ray study of 5-phenyl-l-oxa-4,6-dithia-5-bismocane revealed structure (74). The Bi—O interaction ensures the conformation shown, in the crystal at any rate. The bismuth coordination sphere is completed by intermolecular sulfur ligands (75) and the intermolecular stacking is shown in (76). 

In the case of three bidentate sulfur ligands, e.g. [Bi(pedt)3]2-EtOH (pedt = 1-pyrrolidinecarbondithioate), more complex structures are formed. The dimer contains two differently coordinated bismuth atoms one is trigonal prismatic with an extra position on a rectangular face and the other bismuth atom is pentagonal pyramidal. The overall molecular structure is (80).270... 

The high affinity of bismuth for charged sulfur ligands results in the ready generation of bismuth thiolates from a range of bismuth salts and an appropriate thiol, although reaction of Na(Li)SR with Bids or of BiPh3 with RSH have also been Examples are... 

Bismuth compounds with three organyl sulfur ligands... 

Similar unfavorable constants can be obtained for the other cases. A successful agent in complexing the Hg(II) is BAL (British anti-Lewisite), 2,3-dimercaptopropanol, with potent sulfur ligands for the mercury, and also for arsenic, antimony, bismuth, and gold. It is injected intramuscularly in 10% solution in peanut oil at a dose rate of 3 mg/kg of body weight every 4 hr for two days, and after that at decreasing frequency until recovery. 

Chart 3. Sulfur donor derivatives used as ligands on bismuth. 

Chart 5. Multifunctional ligands for bismuth with sulfur donors. 

Obridgmg 2.78(1) A], but also effect a bridge in the homoleptic anion. The cation predictably involves bridging thiourea sulfur atoms [Bi-S 2.909(5) and 3.132(5) A] as well as two terminal thiourea ligands [Bi-S 2.677(5) and 3.152(6) A], In contrast, Bi(CH3COO]3(tu)3 is molecular in the solid state with bismuth in a nine-coordinate environment composed of three bidentate acetate groups [avg. Bi-0 2.509(4) A] and three thiourea sulfur atoms [avg. Bi-S 3.061(2) A] in a fac arrangement. 

Complexes of bismuth chloride with 2 equiv of the AT,AT-substituted dithioxamide ligands of the general formulas [BiCl3 RNHC(S)C(S) NHR 2] (R = Me, Et, Pr, nBu, CH2Ph) likely involve five-membered chelate interactions (123) as demonstrated by the structurally characterized example [BiCl3 EtNHC(S)C(S)NHEt 2] Me2CO, which involves a seven-coordinate pentagonal bipyramidal environment for bismuth (124), with chlorine atoms in axial positions [Bi-Cl 2.635(10) and 2.717(1) A] and one equatorial [Bi-Cl 2.651(12) A] with four sulfur centers [Bi-S 2.818(13)-3.042(12) A],... 

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