The density functional theory (DFT) method has been used to study the electronic communication in strongly interacting oxo-bridged di-{Mo-II,Mo-I(NO+)}(3+,2+) complexes stabilized by tris(3-methylpyrazol-1-yl)borate, [Tp(Me)](-) (dihydroxy 1' and its modified analogs), having fully localized valences on the two Mo centers (Class l), despite a short (ca. 3.8 angstrom) Mo center dot center dot center dot Mo distance. Structural and electrochemical (separation between the redox potentials Delta(red/ox)E1/2) properties and IR spectra (in particular the 111,10 frequencies) obtained from the B3LYP calculations for 1' are successfully related to experimental values. Strongly twisted geometry with the (O)N-Mo1 center dot center dot center dot Mo2-N(O) angle close to 90 degrees (confirmed by DFT modeling performed for 1'(-1.0+1) and X-ray diffraction study of [{Mo(NO)-(Tp(Me2))(OH)}(2)(mu-O)](-) (1) presented herein) is a common, though so far not fully understood, structural feature of this class of mu-oxo species, in contrast to the closely related {Mo-V(=O)}(3+) analogs. This study shows that the orthogonality of the local equatorial planes for the two Mo centers may be rationalized by the electronic structure, namely from the balance between the destabilizing repulsion of the Mo-based (d, pi(star)(x))b electron pairs versus a favorable but relatively weak electron delocalization. Strongly repelling electron pairs avoid each other, which enforces the twisted geometries and blocks the electron delocalization. Steric hindrance (a nonbonding repulsion of the adjacent Tp(x) ligands and the weak hydrogen-bonding interactions, i.e., OH center dot center dot center dot ON, OH center dot center dot center dot OH, and C-H center dot center dot center dot O-(NO/OH)) is shown not to be decisive since neither the removal of the inner 3-Me groups of [Tp(Me)](-) in complex 1' nor the substitution of OH groups by OCH3 ligands did substantially influence the dihedral twist angle in the minimum energy structure. Yet the relative orientation of the {Mo(NO)}(2+'3+) cores along with the position of the bridging oxygen (significantly bent upon reduction) controls the prospective intramolecular through-bond electron transfer in the mixed valence form. Our DFT modeling demonstrates that a maximum delocalization (via a hole-transfer mechanism) of the unpaired electron in 1'(-) measured as a spin population on the nonreduced Mo2 center, is achieved for the structure with a torsional deflection of 23 degrees, at a cost of 16.5 kcal/mol. These results show that the electron exchange along the Mo-O-Mo array in the originally fully valence-trapped {17e:16e}(-) complexes may be controlled and can be thermally activated (e.g., using a high-boiling solvent or by irradiation at ca. 50-200 cm(-1)).