Diorganylbismuth compounds with Bi-N bonds

Bis(4-methylphenyl)bismuth A -(4-methylphenyl)sulfonylamide 4 is obtained in moderate yield by the reaction of tris(4-methylphenyl)bismuth [A -(4-methylphenyl)sulfonyl]imide with anise alcohol or cinnamyl alcohol [96JCR(S)24]. This amide is insoluble in benzene, but soluble in chloroform, and not so sensitive to oxygen md moisture in the solid state. However, it slowly decomposes to tris(4-methylphenyl)bismuthine and a white powdery deposit when the amide is stood in CDCI3. 

By contrast, (4-methylphenyl)[2-(4,4-dimethyl-2-oxazolin-2-yl)phenyl]-bismuth 7/-(trifluoromethanesulfonyl)amide (5) is prepared in quantitative yield by the action of a 1 1 molar mixture of potassium tert-butoxide and trifluoromethanesulfonyl amide (TfNH2) on chloro(4-methylphenyl)[2-(4,4-dimethyl-2-oxazolin-2-yl)phenyl]bismuthine in THF at room temperature [98OM1013]. In contrast to amide 4, the amide 5 is thermally stable and does not disproportionate when stood in a solution. 

Diphenylbismuth bis(methanesulfonyl)amide (6) is prepared by an acido-lysis of Ph Bi with HN(S02Me)2 in 85% yield. Compound 6 can be prepared by a reaction of Ph2BiCl with AgN(S02Me 2 in 26% yield 

By metathesis between bromo(di-r r/-butyl)bismuthine Bu2BiBr and dipotassium sulfurdiimide K2SN2, bis(di-tert-butylbismuthino)sulfurdiimide Bu2BiN=S=NBi Bu2 is formed as yellow crystals in 10% yield. This compound is labile and decomposes slowly at room temperature. It shows reversible thermochromism on cooling. Under an inert atmosphere at —40°C 

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