Probing the influence of the Tp ligand on reactions of Pt(II) and Pt(IV)

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  • Probing the influence of the Tp prime ligand on reactions of Pt(II) and Pt(IV)
Last Modified
  • March 22, 2019
Creator
  • Engelman, Kristi L.
    • Affiliation: College of Arts and Sciences, Department of Chemistry
Abstract
  • Transformations of platinum(II) to platinum(IV) using organic reagents have been studied. A tridentate ligand system, hydridotris(3,5-dimethylpyrazolyl)borate - Tp prime was shown to promote reactions at the platinum center. Three types of organic reagents have been investigated: alkynes, carbon monoxide, and isonitriles. Reaction of the Tp prime PtMe fragment with terminal alkynes results in eta2-binding of the alkyne. Oxidative addition of the alkyne occurs upon gentle heating. Kinetic studies indicate that electron donating groups on the alkyne increase the rate of oxidative addition and that approaching the transition state increases the entropy. The proposed mechanism of oxidative addition proceeds through a transition state in which the third arm of the Tp prime ligand is dechelated, a process that would be made easier by an electron donating group on the alkyne. In contrast, the reaction of alkynes (both terminal and internal) with the Tp prime PtPh fragment does not produce eta2-bound alkyne adducts. Instead, phenyl migration to the alkyne followed by ortho C-H bond activation occurs resulting in formation of unsaturated metallacycles. Conversion of Tp prime Pt(Me)(CO) to the acyl complex, Tp prime Pt(C(Me)=O)MeH has been accomplished by nucleophilic attack with MeLi followed by addition of HCl. The Pt(IV) acyl complex reacts with adventitious water in the presence of CO to produce the acyl dihydride product, Tp prime Pt(C(Me)=O)H2, from a proposed metal mediated water gas shift reaction. Upon addition of acid, formation of dihydrogen is observed. An analogous carboxamido complex, Tp prime Pt((C=O)NHR)Me2, has also been synthesized. Deprotonation of the carboxamido ligand followed by acidification produces Tp prime PtMe2H, presumably after elimination of free isocyanate. Reaction of the Tp prime PtMe fragment with 2,6-dimethylphenyl isonitrile produces a four-coordinate sigma-bound isonitrile complex. This complex is susceptible to nucleophilic attack at the carbon of the isonitrile, producing an iminoacyl moiety. Protonation at the nitrogen of the iminoacyl complex results in an aminocarbene complex. The availability of the lone pair at the nitrogen of the free pyrazole arm of the Tp prime ligand provides access to rare six-coordinate iminoacyl and aminocarbene complexes.
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  • In Copyright
Advisor
  • Templeton, Joseph
Degree granting institution
  • University of North Carolina at Chapel Hill
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  • Open access
Date uploaded
  • October 11, 2010

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