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• W2783205248 abstract "Four new Zeise’s family ions with mixed-halide ligands, i.e., PtClnX3–n(C2H4)− (X = Br, I; n = 1, 2), were synthesized via ligand-exchange reactions of KX salts with KPtCl3(C2H4) in aqueous solutions, and were detected in vacuum via electrospray ionization mass spectrometry. Their photoelectron spectra reveal a series of well-resolved spectral peaks with their electron binding energies (EBEs) decreasing with increasing halide size, with I having a much stronger effect than Br, i.e., 4.57 (−Cl3) > 4.56 (−Cl2Br) > 4.53 (−ClBr2) > 4.34 (−Cl2I) > 4.30 eV (−ClI2). Ab initio electronic structure calculations including spin–orbit coupling (SOC) predict that the cis- and trans-isomers are nearly isoenergetic with the cis-isomer for −Cl2X and the trans-isomer for −ClX2 slightly favored, respectively. Excited-state spectra calculated with time-dependent density functional theory (TDDFT), and their comparison with the observed ones, suggest that for each species both the cis- and trans-configurations coexist in the experiments and contribute to the observed spectra, a fact that clearly deviates from the prediction of the widely accepted trans-effect, which suggests that only one isomer would have formed." @default.
• W2783205248 created "2018-01-26" @default.
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• W2783205248 date "2018-01-29" @default.
• W2783205248 modified "2023-09-25" @default.
• W2783205248 title "Deviation from the <i>trans</i>-Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl₃(C₂H₄)⁻ with Heavier Halides (Br^–, I^–)" @default.
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• W2783205248 doi "https://doi.org/10.1021/acs.jpca.7b10808" @default.
• W2783205248 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/29338224" @default.
• W2783205248 hasPublicationYear "2018" @default.
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