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Issue 45, 2012
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Acylated cyanoimido-complexes trans-[Mo(NCN){NCNC(O)R}(dppe)2]Cl and their reactions with electrophiles: chemical, electrochemical and theoretical study

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Abstract

Treatment of a dichloromethane solution of trans-[Mo(NCN){NCNC(O)R}(dppe)2]Cl [R = Me (1a), Et (1b)] (dppe = Ph2PCH2CH2PPh2) with HBF4, [Et3O][BF4] or EtC(O)Cl gives trans-[Mo(NCN)Cl(dppe)2]X [X = BF4 (2a) or Cl (2b)] and the corresponding acylcyanamides NCN(R′)C(O)Et (R′ = H, Et or C(O)Et). X-ray diffraction analysis of 2a (X = BF4) reveals a multiple-bond coordination of the cyanoimide ligand. Compounds 1 convert to the bis(cyanoimide) trans-[Mo(NCN)2(dppe)2] complex upon reaction with an excess of NaOMe (with formation of the respective ester). In an aprotic medium and at a Pt electrode, compounds 1 (R = Me, Et or Ph) undergo a cathodically induced isomerization. Full quantitative kinetic analysis of the voltammetric behaviour is presented and allows the determination of the first-order rate constants and the equilibrium constant of the trans to cis isomerization reaction. The mechanisms of electrophilic addition (protonation) to complexes 1 and the precursor trans-[Mo(NCN)2(dppe)2], as well as the electronic structures, nature of the coordination bonds and electrochemical behaviour of these species are investigated in detail by theoretical methods which indicate that the most probable sites of the proton attack are the oxygen atom of the acyl group and the terminal nitrogen atom, respectively.

Graphical abstract: Acylated cyanoimido-complexes trans-[Mo(NCN){NCNC(O)R}(dppe)2]Cl and their reactions with electrophiles: chemical, electrochemical and theoretical study

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Publication details

The article was received on 20 Apr 2012, accepted on 23 May 2012 and first published on 24 May 2012


Article type: Paper
DOI: 10.1039/C2DT30867C
Citation: Dalton Trans., 2012,41, 13876-13890
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    Acylated cyanoimido-complexes trans-[Mo(NCN){NCNC(O)R}(dppe)2]Cl and their reactions with electrophiles: chemical, electrochemical and theoretical study

    E. C. B. A. Alegria, M. F. C. Guedes da Silva, M. L. Kuznetsov, S. M. P. R. M. Cunha, L. M. D. R. S. Martins and A. J. L. Pombeiro, Dalton Trans., 2012, 41, 13876
    DOI: 10.1039/C2DT30867C

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