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• W2024525101 endingPage "1003" @default.
• W2024525101 startingPage "998" @default.
• W2024525101 abstract "A new Pt2II,II complex with the formula Pt2(TPAB)Me4 (1), where TPAB = 1,2,4,5-tetrakis(5-(p-C7H15Ph)-7-azaindol-1-yl)benzene, has been synthesized. This molecule has excellent solubility in common solvents, which enabled our investigation of its reactions with a variety of oxidants to form Pt2IV,IV species and the reverse reactions of the Pt2IV,IV species back to 1 via reduction. Despite the lack of direct Pt···Pt interactions, the two Pt centers in 1 display distinct bimetallic cooperativity mediated by the central phenyl ring of the TPAB ligand. The most unusual finding is that the reactivity of 1 with MeOTf is highly dependent on the amount of molecular oxygen present in the reaction medium. In the absence of O2, the reaction of 1 with MeOTf produced [Pt2IV,IV(TPAB)Me6][OTf]2 (6), while in the presence of O2, complex 7, Pt2IV,IV(TPAB)Me4(OTf)2, was obtained. Compound 1 was found to react readily with O2 at one atmosphere and ambient temperature to produce an insoluble and not yet fully characterized solid that further reacts with MeOTf to produce 7 quantitatively. NMR and single-crystal X-ray diffraction analyses established that the two PtIV centers in 6 are five-coordinate with a square-pyramidal geometry, while in 7 the two PtIV centers are six-coordinate with an octahedral geometry. Most significantly, the central phenyl ring of the TPAB ligand was transformed to a cyclohexyldienyl in 7, while it remains unchanged in 6. Complex 1 also reacts readily with other oxidants such as CHCl3, PhICl2, Br2 (CBr4), I2, and H2O2 to produce Pt2IV,IV(TPAB)Me4X2 (X = Cl, 2; Br, 3; I, 4; OH, 5). The structures of 2−5 are similar to that of 7, showing the generality of the central phenyl ring mediated oxidation of the Pt2II,II system. Complexes 2 and 7 can be reduced and converted back to complex 1 via reactions with BH4−, as established by NMR experiments." @default.
• W2024525101 created "2016-06-24" @default.
• W2024525101 creator A5000788949 @default.
• W2024525101 creator A5057524603 @default.
• W2024525101 creator A5089459816 @default.
• W2024525101 date "2009-12-31" @default.
• W2024525101 modified "2023-10-18" @default.
• W2024525101 title "New Bimetallic Reactivity in Pt₂^II,II/Pt₂^IV,IV Transformation Mediated by a Benzene Ring" @default.
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• W2024525101 doi "https://doi.org/10.1021/om901046p" @default.
• W2024525101 hasPublicationYear "2009" @default.
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