Mechanistic studies of platinum(II)-catalyzed ethylene dimerization: determination of barriers to migratory insertion in diimine Pt(II) hydrido ethylene and ethyl ethylene intermediates |
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Authors: | Shiotsuki Masashi White Peter S Brookhart Maurice Templeton Joseph L |
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Institution: | Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290, USA. |
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Abstract: | The diimine platinum(II) ethylene hydride complex (N/\N)Pt(H)(ethylene)]BAr'4] (1, N/\N = (2,6-Me2C6H3)N=C(An)-C(An)=N(2,6-Me2C6H3)], An = 1,8-naphthalenediyl, Ar' = 3,5-(CF3)2C6H3) was prepared by protonation of the diethyl complex (N/\N)PtEt2 with H(OEt2)2]BAr'4]. The energy barrier to interchange of the platinum hydride with the olefinic hydrogens in 1 was determined to be 19.2 kcal/mol by spin saturation transfer experiments. Complex 1 initiates ethylene dimerization; the ethyl ethylene complex (N/\N)Pt(Et)(ethylene)+ (2) has been identified as the catalyst resting state. Trapping of 1 by ethylene to yield 2 is a second-order process; kinetic studies suggest this occurs via trapping of a reversibly formed beta-agostic ethyl complex. Complex 2 has been isolated and characterized by X-ray crystallography. The barrier to migratory insertion of 2, the turnover-limiting step in catalysis, was determined to be 29.8 kcal/mol. The 1-butene hydride complex, (N/\N)Pt(H)(1-butene)+ (3), is a key intermediate in the dimerization cycle and has also been isolated and characterized. Surprisingly rapid rates of degenerate associative exchange of free ethylene with bound ethylene in complexes 1 and 2 as well as the rate of degenerate exchange of free nitrile with bound nitrile in (N/\N)Pt(Et)(CH3CN)+ are reported. |
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