Matrix isolation and cryogenic thin film approaches have been employed for the synthesis, isolation, and characterization of 1:1 and 1:2 complexes of (CH3)(2)Zn with group V and VI alkyls and acetone. A high yield of complex was formed for each system, and the ratio of 1:1 to 1:2 adduct could be altered by changing concentration and deposition conditions. All of the complexes were characterized by a shifting of sensitive vibrational modes of the (CH3)(2)Zn subunit, along with perturbation to certain vibrational modes of the base. The ZnC2 anztisymmetric stretching mode was the most sensitive to complexation, and the magnitude of the shift of this mode was taken as a qualitative indication of the strength of interaction in the complex. The relative shifts also correlated well with the photon affinities of the several bases in the study.