1286744-65-7Relevant academic research and scientific papers
Pt(II) and Pt(IV) amido, aryloxide, and hydrocarbyl complexes: Synthesis, characterization, and reaction with dihydrogen and substrates that possess C-H bonds
Webb, Joanna R.,Munro-Leighton, Colleen,Pierpont, Aaron W.,Gurkin, Joshua T.,Gunnoe, T. Brent,Cundari, Thomas R.,Sabat, Michal,Petersen, Jeffrey L.,Boyle, Paul D.
, p. 4195 - 4211 (2011/06/27)
The Pt(II) amido and phenoxide complexes (tbpy)Pt(Me)(X), ( tbpy)Pt(X)2, and [(tbpy)Pt(X)(py)] [BAr′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 °C results in the formation of the Pt(II) phenylacetylide complex (tbpy)Pt(Me)(C - CPh). 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-NHPh 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′4] and [(tbpy)Pt(OPh)(py)] [BAr′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′4] with ligands that are more labile than pyridine (e.g., NC5F5) results in the formation of the dimer [( tbpy)Pt(μ-NHPh)]2[BAr′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.
