Hydrogen atom, proton and electron transfer self-exchange and cross-reaction rates have been determined for reactions of Os(IV) and Os(III) aniline and anilide complexes. Addition of an H-atom to the Os(IV) anilide TpOs(NHPh)Cl-2 ((OsNHPh)-N-IV) gives the Os(III) aniline complex TpOs(NH2Ph)Cl-2 ((OsNH2Ph)-N-III) with a new 66 kcal mol(-1) N-H bond. Concerted transfer of H-. between (OsNHPh)-N-IV and (OsNH2Ph)-N-III is remarkably slow in MeCN-d(3), with k(H.)(ex) = (3 +/- 2) x 10(-3) M-1 s(-1) at 298 K. This hydrogen atom transfer (HAT) reaction could also be termed proton-coupled electron transfer (PCET). Related to this HAT process are two proton transfer (PT) and two electron transfer (ET) self-exchange reactions, for instance, the ET reactions (OsNHPh)-N-IV + (OsNHPh-)-N-III and (OsNH2Ph+)-N-IV + (OsNH2Ph)-N-III. All four of these PT and ET reactions are much faster (k = 10(3)-10(5) M-1 s(-1)) than HAT self-exchange. This is the first system where all five relevant self-exchange rates related to an HAT or PCET reaction have been measured. The slowness of concerted transfer of H-. between (OsNHPh)-N-IV and (OsNH2Ph)-N-III is suggested to result not from a large intrinsic barrier but rather from a large work term for formation of the precursor complex to H-. transfer and/or from significantly nonadiabatic reaction dynamics. The energetics for precursor complex formation is related to the strength of the hydrogen bond between reactants. To probe this effect further, HAT cross-reactions have been performed with sterically hindered aniline/anilide complexes and nitroxyl radical species. Positioning steric bulk near the active site retards both H-. and H+ transfer. Net H-. transfer is catalyzed by trace acids and bases in both self-exchange and cross reactions, by stepwise mechanisms utilizing the fast ET and PT reactions.