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Molecules 2017, 22(7), 1141; doi:10.3390/molecules22071141

Metal-Mediated Addition of N-Nucleophiles to Isocyanides: Mechanistic Aspects

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, Lisbon 1049-001, Portugal
International Group on Organometallic Chemistry, Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab., 7/9, Saint Petersburg 199034, Russia
Author to whom correspondence should be addressed.
Received: 21 June 2017 / Revised: 6 July 2017 / Accepted: 6 July 2017 / Published: 8 July 2017
(This article belongs to the Section Theoretical Chemistry)
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Despite the long history of the investigation of nucleophilic addition to metal-bound isocyanides, some important aspects of the reaction mechanism remain unclear even for the simplest systems. In this work, the addition of the sp3-N, sp2-N, and mixed sp2/sp3-N nucleophiles (i.e., HNMe2, HN=CPh2, and H2N–N=CPh2, respectively) to isocyanides C≡NR coordinated to the platinum(II) centers in the complexes cis-[Pt(C≡NCy)(2-pyz)(dppe)]+ (2-pyz = 2-pyrazyl, dmpe = Me2PCH2CH2PMe2) and cis-[PtCl2(C≡NXyl)(C≡NMe)] was studied in detail by theoretical (DFT) methods. The mechanism of these reactions is stepwise associative rather than concerted and it includes the addition of a nucleophile to the isocyanide C atom, deprotonation of the nucleophilic moiety in the resulting intermediate, and protonation of the isocyanide N atom to give the final product. The calculated activation energy (ΔG) of all reactions is in the range of 19.8–22.4 kcal/mol. View Full-Text
Keywords: isocyanides; nitriles; nucleophilic addition; DFT calculations; activation of small molecules; reaction mechanism; carbenes isocyanides; nitriles; nucleophilic addition; DFT calculations; activation of small molecules; reaction mechanism; carbenes

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Kuznetsov, M.L.; Kukushkin, V.Y. Metal-Mediated Addition of N-Nucleophiles to Isocyanides: Mechanistic Aspects. Molecules 2017, 22, 1141.

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