Synthesis, Stereochemistry, and Solution Dynamics of Heterobimetallic Complexes with Metals Connected by Dithioxamides in κ-S,S‘ κ-N,N‘ Binucleation Mode. The Molecular Structure of [2-(Diphenylphosphino)pyridine-Pt-Cl-(<i>μ</i>-<i>N</i>,<i>N</i>‘- dibenzyldithioxbisamidato-κ-<i>S</i>,<i>S</i>‘-Pt-κ-<i>N</i>,<i>N</i>‘-Pd)(<i>η</i>³-allyl)Pd]

Dehydrohalogenation of dithioxamide complexes {(PN)ClPt(H2R2N2C2S2)+(Cl-)} (PN = 2-(diphenylphosphino)pyridine; H2R2N2C2S2 = secondary dithioxamides, H2DTO, R = ethyl, 1; R = benzyl, 2; R = {S}-phenylethyl, 3) leads to the dithioxamidates [(PN)Cl]Pt(HR2N2C2S2)] (HR2N2C2S2- = dialkyldithioxamidate, HDTO) 4−6, which can act as ligands (complexes as ligands). In fact, after deprotonation, they can easily promote chloro-bridge splitting reaction of [Pd(η3-allyl)(μ-Cl)]2 leading to heterobimetallic complexes of formula [(PN)ClPt(μ-R2N2C2S2-κ-S,S-Pt-κ-N,N-Pd)Pd(η3-allyl)]; R2N2C2S22- = dialkyldithioxbisamidate, DTO; R = ethyl, 7; R = benzyl, 8; R = {S}-phenylethyl, 9. These complexes are chiral; hence, 7 and 8 have been synthesized as racemates, and 9 as an equimolar diastereomeric mixture owing to the optically pure {S}-phenylethyl substituent. Upon warming, 7 and 8 racemize, and 9 epimerizes. The isomerization processes may be explained by a mechanism that involves (a) breaking of one of the two Pd−N bonds; (b) rotation around the remaining Pd−N bond; (c) isomerization of the T-shaped intermediate; and (d) remaking of the Pd−N bond. The solid structure of complex 8 has been determined by X-ray single-crystal diffraction analysis.