The new, unsymmetrical dithiocarbamate ligands, KS2CN(CH2CH-CH2)Me and KS2CN(CH2C=CH)Me, are formed from the respective amines on reaction with KOH and carbon disulfide. The homoleptic complexes [Ni{S2CN(CH2CH-CH2)Me}(2)] and [M{S2CN(CH2C=CH)Me}(2)] (M = Ni, Pd, Pt) are formed on reaction with suitable metal precursors. Conversion between the two pendant functionalities was confirmed by hydrogenation of [Ni{S2CN(CH2C=CH)Me}(2)] to yield [Ni{S2CN(CH2CH-CH2)Me}(2)]. The monodithiocarbamate compounds of group 8, 10, and 11 metals, [Ru{S2CN(CH2CH-CH2)Me}(dppm)(2)](+), [Ru(CH-CHC6H4Me-4){S2CN(CH2CH-CH2)Me}(CO)(PPh3)(2)], [Ni{S2CN(CH2CH-CH2)Me}(dppp)](+), and [Au{S2CN(CH2CH-CH2)Me}(PPh3)] were formed successfully. Using KS2CN(CH2C=CH)Me, the complex [Ru{S2CN(CH2C=CH)Me}(dppm)(2)](+) was obtained from cis-[RuCl2(dppm)(2)]. One palladium example, [Pd{S2CN(CH2C=CH)Me}(PPh3)(2)](+), was also isolated in low yield. However, under the typical conditions employed, a rearrangement reaction prevented isolation of further group 10 propargyl-dithiocarbamate products. Over the extended reaction time required, Me(HC=CCH2)NCS2- was found to undergo a remarkable, atom-efficient cyclization to form the thiazolidine-2-thione, H2C-CCH2N(Me)C(-S)S, in high yield, with MeC-CHN(Me)C(-S)S as the minor product. The reactivity of the pendant triple bonds in [Ni{S2CN(CH2C=CH)Me}(2)] was probed in the reaction with [RuH(CO)(S2P(OEt)(2))(PPh3)(2)] to form the trimetallic example [Ni{S2CN(Me)CH2CH-CHRu(CO)(S2P(OEt)(2))(PPh3)(2)}2], while the copper(I) catalyzed reaction with benzylazide yielded the triazole product, [Ni{S2CN(Me)CH2(C2HN3)Bz}(2)]. KS2CN(CH2C=CH)Me was also used to prepare the gold nanoparticles, Au@S2CN(CH2C=CH)Me. Structural studies are reported for [Ru(CH-CHC6H4Me-4){S2CN(CH2CH-CH2)Me}(CO)(PPh3)(2)] and [Ru{S2CN(CH2C=CH)Me}(dppm)(2)]PF6.