Acylated cyanoimido-complexes trans-[Mo(NCN){NCNC(O)R}(dppe)(2)]Cl and their reactions with electrophiles: chemical, electrochemical and theoretical study.
Treatment of a dichloromethane solution of trans-[Mo(NCN){NCNC(O)R}(dppe)(2)]Cl [R = Me (1a), Et (1b)] (dppe = Ph(2)PCH(2)CH(2)PPh(2)) with HBF(4), [Et(3)O][BF(4)] or EtC(O)Cl gives trans-[Mo(NCN)Cl(dppe)(2)]X [X = BF(4) (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 = BF(4)) 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.
Centro de Química Estrutural, Instituto Superior Técnico, Technical University of Lisbon, Portugal.
Elisabete C B A
EC
Alegria
M Fátima C
MF
Guedes da Silva
Maxim L
ML
Kuznetsov
Sónia M P R M
SM
Cunha
Luísa M D R S
LM
Martins
Armando J L
AJ
Pombeiro
D000215:Acylation; D055664:Electrochemical Techniques; D007094:Imides / Q000737:chemistry*; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism
D007094:Imides; D009942:Organometallic Compounds; D008982:Molybdenum