Reactivity of bulky tris(Phenylpyrazolyl) methanesulfonate copper(I) complexes towards small unsaturated molecules
Data(s) |
08/09/2015
08/09/2015
01/09/2012
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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. |
Identificador |
ROCHA, 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) 0022-328X http://hdl.handle.net/10400.21/5119 10.1016/j.jorganchem.2012.03.022 |
Idioma(s) |
eng |
Publicador |
Elsevier |
Relação |
Fundação para a Ciência e a Tecnologia (FCT), Portugal PPCDT program (FEDER) - PTDC/QUI-QUI/102150/2008 PPCDT program (FEDER) - PTDC/QUI-QUI/098760/2008 PPCDT program (FEDER) - PTDC/QUI-QUI/109846/2009 PPCDT program (FEDER) - PEst-OE/QUI/UI0100/2011 Group V of Centro de Química Estrutural - SFRH/BD/23187/2005 Group V of Centro de Química Estrutural - BL-CQE/2010-014 Instituto Superior Técnico (IST) |
Direitos |
closedAccess |
Palavras-Chave | #Tris(pyrazolyl)methanesulfonate Ligand #Copper Complexes #Isocyanide #Carbon Monoxide #3-Iminoisoindolin-1-One #Catalytic Peroxidative Oxidation #Coordination Chemistry #Rhenium Complexes #Mild Conditions #1,3,5-Triazapentadienato Complexes #Structural-Characterization #Spectroscopic Properties #Cyclohexane Oxidation #Crystal-Structures #Redox Properties |
Tipo |
article |