A cooperative pathway for water activation using a bimetallic Pt0-CuI system
| Autor: | Sedigheh Abedanzadeh, Reza Kia, Hamidreza Samouei, Hamid R. Shahsavari, Z. Hendi, Stefano Zacchini, N. K. Khaledi, Sirous Jamali |
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| Přispěvatelé: | Jamali, S, Abedanzadeh, S., Khaledi, N.K., Samouei, H., Hendi, Z., Zacchini, S., Kia, R., Shahsavari, H.R. |
| Jazyk: | angličtina |
| Rok vydání: | 2016 |
| Předmět: |
chemistry.chemical_element
010402 general chemistry Photochemistry 01 natural sciences Inorganic Chemistry DENSITY-FUNCTIONAL THEORY chemistry.chemical_compound Hexafluorophosphate Pyridine BASES PLATINUM GAS SHIFT REACTION 010405 organic chemistry Ligand Hydride CATALYSIS HYDRATION Nuclear magnetic resonance spectroscopy ONLY LEWIS PAIRS 0104 chemical sciences Crystallography chemistry SELECTIVITY Intramolecular force SILVER(I) COMPLEXES Platinum Phosphine |
| Popis: | A mixture of the platinum(0) complex [Pt(PtBu3)2] and tetrakis(acetonitrile)copper(I) hexafluorophosphate in acetone activated a water molecule and gave the hydride platinum(II) complex [PtH(CH3CN)(PtBu3)2]PF6, 1, and the hydroxide Cu(I) species. The crystal structure of complex 1 was determined by X-ray crystallography, indicating a distorted square planar geometry around the platinum center. Although three possible mechanisms are proposed for this transformation, monitoring of the reaction using NMR spectroscopy at low temperature reveals that a cooperative pathway involving formation of a Pt0–CuI dative bond complex is the most probable pathway. The hydride platinum complex 1 is stable in acidic and neutral conditions but undergoes intramolecular C–H activation in the presence of pyridine. Monitoring of the reaction using 1H and 31P NMR spectroscopy shows that a cyclometalation reaction of one of the phosphine ligands is followed by displacement of a second phosphine ligand by pyridine to give the cyclometalated platinum(II) complex, [Pt(κ2PC-PtBu2CMe2CH2)(py)2], 4. The structure of 4 in solution and solid state phases was determined using NMR spectroscopy and X-ray crystallography, respectively. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
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