Rocha, Bruno G. M.Wanke, RiccardoSilva, Maria de Fátima Costa Guedes daLuzyanin, Konstantin V.Martins, LuisaSmolenski, PiotrA.J.L. Pombeiro2015-09-082015-09-082012-09ROCHA, B. G. M.; [et al] – Reactivity of bulky tris(Phenylpyrazolyl) methanesulfonate copper(I) complexes towards small unsaturated molecules. Journal of Organometallic Chemistry. ISSN: 0022-328X. Vol. 714 (2012)0022-328Xhttp://hdl.handle.net/10400.21/5119Reaction 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.engTris(pyrazolyl)methanesulfonate ligandCopper complexesIsocyanideCarbon monoxideIminoisoindolin-1-OneCatalytic peroxidative oxidationCoordination chemistryRhenium complexesMild conditionsTriazapentadienato complexesStructural-characterizationSpectroscopic propertiesCyclohexane oxidationCrystal-structuresRedox propertiesjournal article10.1016/j.jorganchem.2012.03.022