The reaction between W-2((TPB)-P-i)(4), where (TPB)-P-i = 2,4,6-triisopropylbenzoate, and 2 equiv of 4-isonicotinic acid (nicH) yields the compound W-2((TPB)-P-i)(2)(nic)(2), 2, and (TPBH)-P-i. Compound 2 is related to the previously reported molybdenum analog, Mo-2((TPB)-P-i)(2)(nic)(2), 1. Compounds 1 and 2 react with 2 equiv of B(C6F5)(3) in THF to form the adducts M-2((TPB)-P-i)(2)(nic-B(C6F5)(3))(2), 1B (M = Mo) and 2B (M = W), which have been crystallographically characterized as solvates M-2((TPB)-P-i)(2)(nic-B(C6F5)(3))(2)center dot 2THF n-hexane. Compounds 1 and 2 are intensely colored due to M-2 delta to pi* MLCT transitions, and upon complexation with B(C5F5)(3) to give 1B and 2B, these bands shift to lower energy and gain in intensity. Each compound shows two one-electron ligand-based reductions with a Delta E-1/2 = 120(1), 300 (1B), 440 (2), and 650 mV (2B). The larger Delta E-1/2 values for the tungsten compounds reflect the greater orbital mixing of the metal 5d-based M2 delta and the nic pi* LUMO. Reduction of solutions of 1B and 2B with (C5F5)(2)Co leads to the anions 1B(-) and 2B(-), which have been characterized spectroscopically by electron paramagnetic resonance (EPR) and UV-vis-NIR absorption. The EPR spectra of 1B(-) and 2B(-) are consistent with ligand-based (i.e., organic) radicals. The electronic spectra contain low-energy narrow charge resonance (IVCT) bands at 3800 (1B(-)) and 4500 cm(-1) (2B(-)), consistent with fully delocalized mixed valence radical anions. The results are compared with electronic structure calculations and with the spectral features of the metal-centered delocalized mixed valence radical cations [((BuCO2)-C-t)(3)M-2](2)center dot mu(2)-(O2C-CO2)(+), to which they are remarkably similar, as well as with other organic-based mixed valence systems.