The EPR spectra of [Ru(NH3)(5)(H2O)](TFMS)(3) and [Os(NH3)(5)(H2O)](TFMS)(3) (TFMS = trifluoromethanesulfonate) have been measured for a range of temperatures for the solid powders and frozen solutions. The g parallel to axis for the "axial" spectrum observed is shown to be perpendicular to the M-O bond axis, as it is perpendicular to the antibonding MO that interacts in a pi fashion with the water molecule. The H-1 NMR of both compounds in 1,2-propanediol carbonate has been obtained over a range of temperatures, and the resonances for axial ammonia, equatorial ammonia, and the bound water in the complex cation have been identified. Using the experimental g values obtained from EPR and an improved equation that uses all t(2) states, the dipolar component of the shift has been calculated and used to find the contact portion of the paramagnetic shift. An improved equation for the contact shift has been developed which separates the spin contribution into the d(xz), d(yz), and d(xy) portions and this theory applied to the measured contact shifts. Values for three hyperfine constants have been obtained, the A(NH3) constant for the MOs that do not pi interact with the water molecule, the A(NH3) constant for the MO that does pi interact, and the A(H2O) for the MO that does pi interact. The spin transfer for the ammonia ligand protons is by hyperconjugation giving a positive A, and for the water proton it is mainly by covalent transfer of spin to the nonbonding p orbital with polarization of the spin on the proton giving a negative A.