Reaction of the 17-electron radical Cr-.(CO)(3)CP* (CP* = C5Me5) with 0.5 equiv of 2-aminophenyl disulfide [(o-H-2-NC6H4)(2)S-2] results in rapid oxidative addition to form the initial product (o-H2N)C6H4S-Cr(CO)(3)Cp*. Addition of a second equivalent of Cr-.(CO)(3)CP* to this solution results in the formation of H-Cr(CO)(3)Cp* as well as 1/2[{eta(2)-0- (mu-NH)C6H4S}CrCP*](2). Spectroscopic data show that (o-H2N)C6H4S-Cr(CO)(3)Cp* loses CO to form {eta(2)-(o-H2N)C6H4S}Cr(CO)(2)CP*. Attack on the N-H bond of the coordinated amine by Cr-.(CO)(3)CP* provides a reasonable mechanism consistent with the observation that both chelate formation and oxidative addition of the N-H bond are faster under argon than under CO atmosphere, The N-H bonds of uncoordinated aniline do not react with Cr-.(CO)(3)CP*. Reaction of the 2 mol of Cr-.(CO)(3)CP* with 1,2-benzene dithiol [1,2-C6H4(SH)(2)] yields the initial product (o-HS)C6H4S--Cr(CO)(3)Cp* and 1 mol of H-Cr(CO)(3)Cp*. Addition of 1 equiv more of Cr-.(CO)(3)CP* to this solution also results in the formation of 1 equiv of H-Cr(CO)(3)CP*, as well as the dimeric product 1/2[{eta(2)-o-(mu-S)C6H4S}-CrCP*](2). This reaction also occurs more rapidly under Ar than under CO, consistent with intramolecular coordination of the second thiol group prior to oxidative addition. The crystal structures of [{eta(2)-o-(mu-NH)C6H4S}CrCP*](2) and [{eta(2)-o-(mu-S)C6H4S}CrCP*](2) are reported.