The preparation of two new families of hexanuclear rhenium cluster complexes containing benzonitrile and phenyl-substituted tetrazolate ligands is described. Specifically, we report the preparation of a series of cluster complexes with the formula [Re(6)Se(8)(PEt(3))(5)L](2+) where L = benzonitrile, p-aminobenzonitrile, p-methoxybenzonitrile, p-acetylbenzonitrile, or p-nitrobenzonitrile. All of these complexes undergo a [2 + 3] cycloaddition with N(3)(-) to generate the corresponding [Re(6)Se(8)(PEt(3))(5)(5-(p-X-phenyl)tetrazol-2-yl)](+) (or [Re(6)Se(8)(PEt(3))(5)(2,5-p-X-phenyltetrazolate)](+)) cluster complexes, where X = NH(2), OMe, H, COCH(3), or NO(2). Crystal structure data are reported for three compounds: [Re(6)Se(8)(PEt(3))(5)(p-acetylbenzonitrile)](BF(4))(2)•MeCN, [Re(6)Se(8)(PEt(3))(5)(2,5-phenyltetrazolate)](BF(4))•CH(2)Cl(2), and [Re(6)Se(8)(PEt(3))(5)(2,5-p-aminophenyltetrazolate)](BF(4)). Treatment of [Re(6)Se(8)(PEt(3))(5)(2,5-phenyltetrazolate)](BF(4)) with HBF(4) in CD(3)CN at 100 °C leads to protonation of the tetrazolate ring and formation of [Re(6)Se(8)(PEt(3))(5)(CD(3)CN)](2+). Surprisingly, alkylation of the phenyl and methyl tetrazolate complexes ([Re(6)Se(8)(PEt(3))(5)(2,5-N(4)CPh)](BF(4)) and [Re(6)Se(8)(PEt(3))(5)(1,5-N(4)CMe)](BF(4))) with methyl iodide and benzyl bromide, leads to the formation of mixtures of 1,5- and 2,5-disubstituted tetrazoles.