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Reactivity of bulky tris(Phenylpyrazolyl) methanesulfonate copper(I) complexes towards small unsaturated molecules

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Resumo:Reaction of the tris(3-phenylpyrazolyl)methane sulfonate species (Tpms(Ph))Li with the copper(I) complex [Cu(MeCN)(4)][PF6] affords [Cu(Tpms(Ph))(MeCN)] 1. The latter, upon reaction with equimolar amounts of cyclohexyl-(CyNC) or 2,6-dimethylphenyl (XylNC) isocyanides, or excess CO, furnishes the corresponding Cu(I)complexes [Cu(Tpms(Ph))(CNR)] (R = Cy 2, Xyl 3) or [Cu(Tpms(Ph))(CO)] 4. The ligated isocyanide in 2 or 3 (or the acetonitrile ligand in 1)is displaced by 3-iminoisoindolin-1-one to afford 5, the first copper(I) complex containing an 3-iminoisoindolin-1-one ligand. The ligated acetonitrile in 1 undergoes nucleophilic attack by methylamine to give the amidine complex [Cu(Tpms(Ph)){MeC(NH)NHMe}] 6, whereas only the starting materials were recovered from the attempted corresponding reactions of 2 and 3 with methylamine. Complexes 1 or 6 form the trinuclear hydroxo-copper(II)species [(mu-Cu){Cu(mu-OH) (2)(Tpms(Ph))}(2)] 7 upon air oxidation in moist methanol. In all the complexes the scorpionate ligand facially caps the metal in the N,N,O-coordination mode.
Autores principais:Rocha, Bruno G. M.
Outros Autores:Wanke, Riccardo; Silva, Maria de Fátima Costa Guedes da; Luzyanin, Konstantin V.; Martins, Luisa; Smolenski, Piotr; A.J.L. Pombeiro
Assunto:Tris(pyrazolyl)methanesulfonate ligand Copper complexes Isocyanide Carbon monoxide Iminoisoindolin-1-One Catalytic peroxidative oxidation Coordination chemistry Rhenium complexes Mild conditions Triazapentadienato complexes Structural-characterization Spectroscopic properties Cyclohexane oxidation Crystal-structures Redox properties
Ano:2012
País:Portugal
Tipo de documento:artigo
Tipo de acesso:acesso restrito
Instituição associada:Instituto Politécnico de Lisboa
Idioma:inglês
Origem:Repositório Científico do Instituto Politécnico de Lisboa

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