Rocha, Bruno G. M.Wanke, RiccardoGuedes da Silva, M. Fátima C.Luzyanin, Konstantin V.Martins, Luísa M. D. R. S.Smolenski, PiotrPombeiro, Armando J. L.2012-10-252012-10-252012-09-01Rocha B G M, Wanke R, Silva, M Fátima C G, Luzyanin K V, Martins L M D R S, Smolenski,P, Pombeiro A J L. Reactivity of bulky tris(phenylpyrazolyl)methanesulfonate copper(I) complexes towards small unsaturated molecules. Journal of Organometallic Chemistry. 2012; 714.0022-328Xhttp://hdl.handle.net/10400.21/1817Reaction 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. (C) 2012 Elsevier B. V. All rights reserved.engTris(pyrazolyl)methanesulfonate LigandCopper ComplexesIsocyanideCarbon Monoxide3-Iminoisoindolin-1-oneCatalytic Peroxidative OxidationCoordination ChemistryRhenium ComplexesMild Conditions1,3,5-Triazapentadienato ComplexesStructural-CharacterizationSpectroscopic PropertiesCyclohexane OxidationCrystal-StructuresRedox Propertiesjournal article