A DFT mechanistic study of the synthesis of trans-Z,Z-[PtIICl(NH3){HN = C(NH2)Me}2]Cl from addition of NH3 to trans-[PtIICl2(N CMe)2]

Girolamo Casella, Silvia Carlotto, Paolo Sgarbossa, Mirto Mozzon, Maurizio Casarin, Girolamo Casella, Roberta Bertani

Research output: Contribution to journalArticlepeer-review

Abstract

The reaction mechanism between trans-[PtIICl2(N^CMe)2] and ammonia to give trans-Z,Z-[PtIICl(NH 3){HN = C(NH2)Me}2]Cl has been studied at DFT level. Results showed that, in dichloromethane solution at263.15 K, the chloride substitution by the ammonia on platinum is a process kinetically more favoured than theammonia nucleophilic addition to the nitrile of about three orders of magnitude, and hence the nucleophilicaddition reaction occurs after. Finally, both nucleophilic addition steps are geometrically driven to give productsin the E configuration even if the final products were experimentally observed in the Z configuration. For trans-Z,Z-[PtIICl(NH3)(N^CMe)2, the isomerization mechanism has been investigated for both nucleophilic additionsteps by considering the deprotonation → isomerization → protonation sequence on nitrogens. The deproto-nation steps could involve either the coordinated or the aminic nitrogen of the formed amidine. Outcomesindicated that the path involving the deprotonation of the aminic nitrogen is favoured.
Original languageEnglish
Pages (from-to)119847-
Number of pages8
JournalInorganica Chimica Acta
Volume511
Publication statusPublished - 2020

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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