The EPR and electronic spectra of d(1)-bent metallocene compounds of the type Cp*(2)TiX, where X is halide, alkoxide, amide, alkyl, or hydride and Cp* = Me(5)C(5), have been studied. Several of these compounds are new, and those with X = N(Me)H and F were characterized by X-ray crystallography. The crystal structure of Cp*2TiN(Me)H showed that the N(Me)H ligand lies on the plane defined by Cp*(centroid)-Ti-Cp*(centroid). This is the sterically most unfavorable conformation but allows maximum Ti-N pi-bonding. The anisotropic frozen solution EPR spectra were analyzed by the method used by Petersen and Dahl for the d(1)-metallocenes, Cp(2)VX(2), which gives g(x), g(y), and g(z). Although the values of g(x) and g(z) are relatively constant throughout the series, the value of g(y) varies with the pi-donor ability of X. The pi-donor series is N(Me)H approximate to NH2 approximate to OMe > OPh approximate to F > N(Me)Ph Cl > Br > I > H. Among the known alkyls, the pi-donor ability was Et > Me > n-Pr approximate to CH(2)CMe(3) > CH2C6H5, which is rationalized, in part, by a beta-agostic interaction in the case of Et. The beta-agostic interaction in Cp*(2)TiEt and in Cp*2TiN(Me)Ph was investigated by variable-temperature EPR spectroscopy giving an enthalpy and entropy for the agostic interaction. For Cp*(2)TiEt the parameters for the agostic interaction are Delta H degrees = -1.93(3) kcal/mol and Delta S degrees = -6.3(2) eu, and for Cp*2TiN(Me)Ph, Delta H degrees = -1.5(1) kcal/mol and Delta S degrees = -7.9(5) eu.