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 eta(2)-salicylato ligand. When the previously reported Bi2Ta2(sal)(4)(Hsal)(4)(OEt)(4) (1) and BiTa4-(mu-O)(4)(sal)(4)(Hsal)(3)((OPr)-Pr-i)(4) (2) are treated with an alcoholic solution of NaBPh4, the compounds [PhBi(Hsal)Ta(sal)(2)(OEt)(2)center dot EtOH](2) (3) and PhBiTa4(mu-O)(4)(Hsal)(2)(sal)(4)(OEt)(4)center dot CH2Cl2 (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)](infinity) (5) is produced instead. This compound was characterized both as a solvent-free crystalline form and 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 anew means for the mild functionalization of bismuthtransition metal heterometallic complexes.