Pt(II) and Pt(IV) Amido, Aryloxide, and Hydrocarbyl Complexes: Synthesis, Characterization, and Reaction with Dihydrogen and Substrates that Possess C鈭扝 Bonds

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• 作者：Joanna R. Webb ; Colleen Munro-Leighton ; Aaron W. Pierpont ; Joshua T. Gurkin ; T. Brent Gunnoe ; Thomas R. Cundari ; Michal Sabat ; Jeffrey L. Petersen ; Paul D. Boyle
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：May 2, 2011
• 年：2011
• 卷：50
• 期：9
• 页码：4195-4211
• 全文大小：1405K
• 年卷期：v.50,no.9(May 2, 2011)
• ISSN：1520-510X

文摘

The Pt(II) amido and phenoxide complexes (^tbpy)Pt(Me)(X), (^tbpy)Pt(X)₂, and [(^tbpy)Pt(X)(py)][BAr鈥?sub>4] (X = NHPh, OPh; py = pyridine) have been synthesized and characterized. To test the feasibility of accessing Pt(IV) complexes by oxidizing their Pt(II) precursors, the previously reported (^tbpy)Pt(R)₂ (R = Me and Ph) systems were oxidized with I₂ to yield (^tbpy)Pt(R)₂(I)₂. The analogous reaction with (^tbpy)Pt(Me)(NHPh) and MeI yields the corresponding (^tbpy)Pt(Me)₂(NHPh)(I) complex. Reaction of (^tbpy)Pt(Me)(NHPh) and phenylacetylene at 80 掳C results in the formation of the Pt(II) phenylacetylide complex (^tbpy)Pt(Me)(C鈮Ph). Kinetic studies indicate that the reaction of (^tbpy)Pt(Me)(NHPh) and phenylacetylene occurs via a pathway that involves [(^tbpy)Pt(Me)(NH₂Ph)][TFA] as a catalyst. The reaction of H₂ with (^tbpy)Pt(Me)(NHPh) ultimately produces aniline, methane, ^tbpy, and elemental Pt. For this reaction, mechanistic studies reveal that 1,2-addition of dihydrogen across the Pt鈭扤HPh bond to initially produce (^tbpy)Pt(Me)(H) and free aniline is catalyzed by elemental Pt. Heating the cationic complexes [(^tbpy)Pt(NHPh)(py)][BAr鈥?sub>4] and [(^tbpy)Pt(OPh)(py)][BAr鈥?sub>4] in C₆D₆ does not result in the production of aniline and phenol, respectively. Attempted synthesis of a cationic system analogous to [(^tbpy)Pt(NHPh)(py)][BAr鈥?sub>4] with ligands that are more labile than pyridine (e.g., NC₅F₅) results in the formation of the dimer [(^tbpy)Pt(渭-NHPh)]₂[BAr鈥?sub>4]₂. Solid-state X-ray diffraction studies of the complexes (^tbpy)Pt(Me)(NHPh), [(^tbpy)Pt(NH₂Ph)₂][OTf]₂, (^tbpy)Pt(NHPh)₂, (^tbpy)Pt(OPh)₂, (^tbpy)Pt(Me)₂(I)₂, and (^tbpy)Pt(Ph)₂(I)₂ are reported.