Ar'BiCl2 [Ar' = 2,6-(Me2NCH2)2C6H3] reacts with two equiv of potassium aryloxide to form Ar'Bi(C6H2tBu2-3,5-O-4), 1 , which contains the unusual dianionic oxyaryl ligand, (C6H2tBu2-3,5-O-4)2-.  The first insertion of CO2 into a Bi�C bond is observed with 1  and this reaction can be combined with the C�H activation that generates 1  to provide a new cyclic process to make 3,5-di-tert-butyl-4-hydroxybenzoic acid from potassium 2,6-di-tert-butylphenoxide, CO2, and [Et3NH][Cl] under mild conditions.  Complex 1  reacts with nitric oxide and the NO delivery reagent Ph3CSNO to generate complexes of a new oximate ligand [ON=(C6H2tBu2O)]1-, formed by formal insertion of NO into the bismuth-carbon bond of the (C6H2tBu2-3,5-O-4)2- dianion. To further study the small molecule activation chemistry of bismuth in unusual coordination environments, a bismuth complex of the ligand N,N',N''-[2,2',2''-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido) has been prepared and will be described.

CO2 and NO activation by a bismuth complex of the unusual oxyaryl dianion, (C6H2tBu2-3,5-O-4)2-

248th National Meeting (2014)

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