Heterometallic bismuth-niobium or tantalum salicylate complexes react with sodium tetraphenylborate  to produce complexes in which one or more aryl groups have been transferred from boron to bismuth with the concomitant displacement of a eta2-salicylato ligand. When the previously-reported Bi2Ta2(sal)4(Hsal)4(OEt)4 (1) and BiTa4(-O)4(sal)4(Hsal)3(OiPr)4 (2) are treated with an alcoholic solution of NaBPh4 the compounds [PhBi(Hsal)Ta(sal)2(OEt)2EtOH]2 (3) and PhBiTa4(-O)4(Hsal)2(sal)4(OEt)4CH2Cl2 (4) are produced (sal = O2CC6H4-2-O2-, Hsal = O2CC6H4-2-OH-). The core geometries of the heterometallic complexes are retained. However if preparations of compound 1 are treated with NaBPh4 without prior isolation of 1, [Ph2BiNb(sal)2(OMe)2] (5) is produced instead. This compound was characterized both as a solvent-free crystalline form as well as one containing a lattice diethyl ether. The compound exhibits a polymeric chain structure that can be viewed as alternating [Ph2Bi]+ and [Nb(sal)2(OMe)2]- units connected via bridging carboxylate groups. The arylation of the bismuth(III) center proceeds smoothly under mild conditions at room temperature affording a new means for the mild functionalization of bismuth-transition heterometallic complexes.

  1. (1)Stavila, V.; Thurston, J. H.; Whitmire, K. H. "Selective Arylation Reactions of Bismuth-Transition Metal Salicylate Complexes," Inorg. Chem. 2009, 48, 6945-6951.