The effect of H-bond donation to the thiolate ligand of (eta(5)-C(5)H(5))Fe(CO)(2)SR (1) to give H-bond adducts (1 small middle dotHX) and eventually protonation to give [(eta(5)-C(5)H(5))Fe(CO)(2)(HSR)](+) (1H(+)()) has been investigated experimentally and computationally. The electronic structures of 1(R = Me), several derivatives of 1(R = Me) small middle dotHX, and 1(R = Me)H(+)() have been investigated using DFT (density functional theory) computational methods. As previously suggested, these calculations indicate the HOMO of 1 is Fedpi-Sppi antibonding and largely sulfur in character. The calculations indicate the electronic structure of 1 is not altered markedly by H-bond donation to the S center, but protonation results in a reorganization of the electronic structure of 1H(+)() and a HOMO that is largely metal in character. The reduction of Fe-S distances upon protonation of 1(R = Ph) to give 1(R = Ph)H(+)() small middle dotBF(4)()(-)() (2.282(2) and 2.258(2) A, respectively), as determined by single-crystal X-ray crystallography, also indicates diminished Fedpi-Sppi antibonding. Using the carbonyl stretching frequencies as a gauge of the donor ability of the thiolate ligand, we conclude that H-bonding has a continuous effect on the donor properties of the thiolate ligand of 1 (i.e., is a function of the pK(a) of the H-bond donor). A discontinuous effect results when the pK(b) of 1 is reached and the complex is protonated. For our study of 1, the maximal effect of H-bonding is about 30% of protonation. Because the position of acid-base equilibrium depends on the relative basicities of the thiolate ligand and the conjugate base of the H-bond donor (and the relative heats of solvation of the acids and their conjugate bases), a true continuum of effects can be anticipated only for systems that are pK-matched in their given environments. Thus, when the conjugate base of the H-bond donor is a stronger base than the thiolate ligand (as in the present case), H-bond donation has a relatively small effect, but protonation triggers a large, discontinuous effect on the electronic structure of 1.