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A referee pointed out that the observed increase in nucleophilic discrimination (0.61 for NCN vs 0.40/0.43)13 could also be due to a decrease in steric discrimination of NCN in comparison with the sterically more hindered reference complexes, and therefore not necessarily due to an electronic effect. If this is the case, a decrease in the ratio of the rate constants in going from unsubstituted to substituted thioureas would be expected since the complex is less sensitive towards steric hindrance on the entering nucleophile. Since such a decrease in comparison with the literature complexes could not be observed, we conclude that the increased nucleophilic discrimination of NCN is mainly due to the electron withdrawing, electrophilicity enhancing π-acceptor effect of the pyridine/phenyl rings.
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2+ has a formal charge of +2 and a calculated NBO charge of +0.83 on the platinum center), we discuss the change in the nucleophilic discrimination in terms of electron density on the platinum center due to electron donation by the better σ-donor phenyl and not in terms of a change in the overall charge on the complex.
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