Reactions are described that interconvert vanadium(IV) oxo-hydroxo complexes [(VO)-O-IV(OH)(R(2)bpy)(2)]BF4 (1a-c) and vanadium(V) dioxo complexes [(VO2)-O-V(R(2)bpy)(2)]BF4 (2a-c) [R(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridine ((t)Bu(2)bpy), a; 4,4'-dimethyl-2,2'-bipyridine (Me(2)bpy), b; 2,2'-bipyridine (bpy), c]. These are rare examples of pairs of isolated, sterically unencumbered, first-row metal-oxo/hydroxo complexes that differ by a hydrogen atom (H+ + e(-)). The V-IV-(t)Bu(2)bpy derivative la has a useful H-1 NMR spectrum, despite being paramagnetic. Complex 2a abstracts H-center dot from organic substrates with weak O-H and C-H bonds, converting 2,6-Bu-t(2)-4-MeO-C6H2OH (ArOH) and 2,2,6,6-tetramethyl-N-hydroxypiperidine (TEMPOH) to their corresponding radicals ArO center dot and TEMPO, hydroquinone to benzoquinone, and dihydroanthracene to anthracene. The equilibrium constant for 2a + ArOH 1a + ArO center dot is (4 +/- 2) x 10(-3), implying that the VO-H bond dissociation free energy (BDFE) is 70.6 +/- 1.2 kcal mol(-1). Consistent with this value, la is oxidized by 2,4,6-(Bu3C6H2O center dot)-Bu-t. All of these reactions are surprisingly slow, typically occurring over hours at ambient temperatures. The net hydrogen-atom pseudo-self-exchange 1 a + 2b reversible arrow 2a + 1b, using the Bu-t-and Me-bpy substituents as labels, also occurs slowly, with K-se = 1.3 x 10(-2) M-1 s(-1) at 298 K, Delta H double dagger = 15 +/- 2 kcal mol(-1), and Delta S double dagger = 16 +/- 5 cal mol(-1) K. Using this k(se) and the BDFE, the vanadium reactions are shown to follow the Marcus cross relation moderately well, with calculated rate constants within 10(2) of the observed values. The vanadium self-exchange reaction is ca. 10(6) slower than that for the related (RuO)-O-IV(py)(bpy)(2)(2+)/(RuOH)-O-III(py)(bpy)(2)(2+) self-exchange. The origin of this dramatic difference has been probed with DFT calculations on the self-exchange reactions of 1c + 2c and on monocationic ruthenium complexes with pyrrolate or fluoride in place of the py ligands. The calculations reproduce the difference in barrier heights and show that transfer of a hydrogen atom involves more structural reorganization for vanadium than the Ru analogues. The vanadium complexes have larger changes in the metal-oxo and metal-hydroxo bond lengths, which is traced to the difference in d-orbital occupancy in the two systems. This study thus highlights the importance of intrinsic barriers in the transfer of a hydrogen atom, in addition to the thermochemical (bond strength) factors that have been previously emphasized.