Compound cis,fac-[Mo(eta(3)-allyl)(CO)(2)(Hdmpz)(3)]BAr'(4) (1) (Hdmpz = 3,5-dimethylpyrazole, Ar' = 3,5-bis(trifluoromethyl)phenyl) undergoes rapid substitution of one of the pyrazole ligands by anions, including the low nucleophilic ReO4-, a reaction that afforded [Mo(OReO3)(eta(3)-allyl)(CO)(2)(Hdmpz)(2)] (2), structurally characterized by X-ray diffraction. The new compounds fac-[Mn(CO)(3)(Hdmpz)(3)]BAr'(4) (4a) and fac-[Mn(CO)(3)(H(t)Bupz)(3)]BAr'(4) (4b) (H(t)Bupz = 3(5)-tert-butylpyrazole) also undergo pyrazole substitution with most anions, and the product from the reaction with nitrate was crystallographically characterized. Compounds 4a,b were found to be substitutionally stable toward perrhenate, and the adducts [Mn(CO)(3)(Hdmpz)(3)]center dot[ReO4] (7a) and [Mn(CO)(3)(H(t)Bupz)(3)]center dot[ReO4]center dot[Bu4N]center dot[BAr'(4)] (7b), crystallographically characterized, display hydrogen bonds between one of the perrhenate oxygens and the N-H groups of two of the pyrazole ligands. The structurally similar adduct [Re(CO)(3)(Hdmpz)(3)]center dot[ReO4] (8) was found to result from the interaction of [Re(CO)(3)(Hdmpz)(3)]BAr'(4) with perrhenate. The reaction of [Re(OTf)(CO)(5)] with 3,5-dimethylpyrazole (Hdmpz) afforded [Re(CO)(5)(Hdmpz)]OTf (9). The reaction of 9 with Hdmpz and NaBAr'(4) yielded [Re(CO)(4)(Hdmpz)(2)]BAr'(4) (10), which was found to be unstable toward chloride anion. In contrast, the new compound fac,cis-[Re(CO)(3)((CNBu)-Bu-t)(Hdmpz)(2)]BAr'(4) (11) is stable in solution in the presence of different anions. Binding constants for 11 with chloride, bromide, and nitrate are 1-2 orders of magnitude lower than those found for these anions and rhenium tris(pyrazole) hosts, indicating that the presence of the third pyrazole ligand is crucial. Compounds fac-[Re(CO)(3)(HPhpz)(3)]BAr'(4) (14) (HPhpz = 3(5)-phenylpyrazole) and fac-[Re(CO)(3)(HIndz)(3)]BAr'(4) (15) (HIndz = indazole) are, in terms of anion binding strength and selectivity, inferior to those with dimethylpyrazole or tert-butylpyrazole ligands.