Room temperature c h activation with pt 0
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Room Temperature C-H Activation with Pt(0). Emmanuel Nicolas Lab “Hétéroéléments et Coordination” Ecole Polytechnique Palaiseau , France. C-H Activation With Pt(II)/Pt(IV). A. Shilov et al. ; Russ. J. Phys. Chem., USSR 1969 , 43 , 1222

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Room Temperature C-H Activation with Pt(0)

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Room temperature c h activation with pt 0

Room Temperature C-H Activation with Pt(0)

Emmanuel Nicolas

Lab “Hétéroéléments et Coordination”

Ecole Polytechnique

Palaiseau, France


C h activation with pt ii pt iv

C-H Activation With Pt(II)/Pt(IV)

A. Shilovet al.; Russ. J. Phys. Chem., USSR1969, 43, 1222

R. A. Perianaet al., Science1998, 280, 560–564

  • Shilov: System

    • 120 °C

  • Periana: CatalyticaTM System

    • 34 bars, 180 °C, 2.5 hours

  • Emmanuel Nicolas


    C h activation with rh ir

    C-H Activation with Rh/Ir

    J. Hartwiget al., J. Am. Chem. Soc.2005, 127, 2538–52

    M. Brookhart, A. Goldman et al., Nature Chem.2011, 3, 167–71

    Hartwig: Rh

    Brookhart and Goldman: Ir

    Emmanuel Nicolas


    Problem position

    Problem position

    • Drastic conditions

      • High Temperature

      • High pressure

      • Long reaction times

    • Increase electron density at metal to ease bond activation

       Reduced metals

    Emmanuel Nicolas


    Halpern pt 0 pt ii

    Halpern: Pt(0)/Pt(II)

    Abis, L.; Sen, A.; Halpern, J. J. Am. Chem. Soc.1978, 100, 2915–6

    • [(PPh3)2PtHMe]

      • Stable up to -50°C

      • Eliminates Methane above -25°C

    Emmanuel Nicolas


    Whitesides

    Whitesides

    Hackett, M.; Ibers, J. A.; Jernakoff, P.; Whitesides, G. M. J. Am. Chem. Soc.1986, 108, 8094–5

    Emmanuel Nicolas


    Bite angle influence

    Bite Angle Influence

    Halpern

    Emmanuel Nicolas


    Bite angle influence1

    Bite Angle Influence

    Whitesides

    Halpern

    Emmanuel Nicolas


    Bite angle influence2

    Bite Angle Influence

    Whitesides

    Halpern

    Emmanuel Nicolas


    Our strategy

    Our Strategy

    Whitesides

    Halpern

    Emmanuel Nicolas


    Our strategy1

    Our Strategy

    Whitesides

    Halpern

    Chemistry

    with Pt(0)

    Chemistry

    with Pt(II)

    Emmanuel Nicolas


    Synthesis of dcpp ptx 2

    Synthesis of [(DCPP)PtX2]

    Overall Yield: 97%

    Issleib, K.; Müller, D.-W. Chem. Ber.1959, 92, 3175–3182

    McDermott, J. X.; White, J. F.; Whitesides, G. M. J. Am. Chem. Soc.1976, 98, 6521–8.

    Emmanuel Nicolas


    Reduction of dcpp ptx 2

    Reduction of [(DCPP)PtX2]

    31P{1H}

    Davies, J. A.; Staples, R. J. Polyhedron1991, 10, 909–917.

    Nicolas, E.; le Goff, X.-F.; Bouchonnet, S.; Mézailles, N. Chem. Comm.2012, 48, 8350–2.

    Emmanuel Nicolas


    Reduction of dcpp ptx 21

    Reduction of [(DCPP)PtX2]

    1H

    Davies, J. A.; Staples, R. J. Polyhedron1991, 10, 909–917.

    Nicolas, E.; le Goff, X.-F.; Bouchonnet, S.; Mézailles, N. Chem. Comm.2012, 48, 8350–2.

    Emmanuel Nicolas


    Reduction of dcpp ptx 22

    Reduction of [(DCPP)PtX2]

    Davies, J. A.; Staples, R. J. Polyhedron1991, 10, 909–917.

    Nicolas, E.; le Goff, X.-F.; Bouchonnet, S.; Mézailles, N. Chem. Comm.2012, 48, 8350–2.

    Emmanuel Nicolas


    Dcpp pth c 7 h 7

    [(DCPP)PtH(C7H7)]

    P-Pt-P: 87.16°

    Nicolas, E.; le Goff, X.-F.; Bouchonnet, S.; Mézailles, N. Chem. Comm.2012, 48, 8350–2

    Hackett, M.; Ibers, J. A.; Jernakoff, P.; Whitesides, G. M. J. Am. Chem. Soc.1986, 108, 8094–5

    Emmanuel Nicolas


    Exchange reactions

    Exchange Reactions

    At room temperature, aryl exchanges statistically with the solvent

    Nicolas, E.; le Goff, X.-F.; Bouchonnet, S.; Mézailles, N. Chem. Comm.2012, 48, 8350–2.

    Emmanuel Nicolas


    Kinetic study disappearance of pt h in c 6 d 6

    Kinetic StudyDisappearance of Pt-H in C6D6

    1H

    Emmanuel Nicolas


    Kinetic study disappearance of pt d in c 6 h 6

    Kinetic StudyDisappearance of Pt-D in C6H6

    31P{1H}

    Integration of part of P-Pt-D coupling motif againstsum of Pt-H and Pt-D

    Emmanuel Nicolas


    Thermochemistry

    Thermochemistry

    k-H= 0.054 L.mol-1.h-1

    k-D= 0.12 L.mol-1.h-1

    Nicolas, E.; le Goff, X.-F.; Bouchonnet, S.; Mézailles, N. Chem. Comm.2012, 48, 8350–2.

    Emmanuel Nicolas


    Pt 0 species

    “Pt(0)” species

    Nicolas, E.; le Goff, X.-F.; Bouchonnet, S.; Mézailles, N. Chem. Comm.2012, 48, 8350–2.

    Room-temperature equilibrium between Pt(II) and Pt(0) species

    Emmanuel Nicolas


    Stability of dcpp pt h c 7 h 7

    Stability of [(DCPP)Pt(H)(C7H7)]

    Leaving complex in toluene for days

    Dimer cristallizes

    Emmanuel Nicolas


    Dihydride dimer

    Dihydride Dimer

    Nicolas, E.; le Goff, X.-F.; Bouchonnet, S.; Mézailles, N. Chem. Comm.2012, 48, 8350–2.

    Emmanuel Nicolas


    Further reactivity arene coupling

    Further reactivity – Arene coupling

    GC/MS Study: Stéphane Bouchonnet, DCMR, Ecole Polytechnique, France

    • Heating in Toluene

    • Biphenyl derivatives detected by GC/MS

      • Mixture of isomers

    Emmanuel Nicolas


    Dft rationalization

    DFT Rationalization

    Benzeneis a reagent and the solvent

     ConsiderΔH ratherthanΔG

    ω-B97X-D // Def2-TZVP (Pt) // 6-31G* (P/C/H) // 6-311+G** (mobile H)

    Emmanuel Nicolas


    Dft rationalization1

    DFT Rationalization

    ω-B97X-D // Def2-TZVP (Pt) // 6-31G* (P/C/H) // 6-311+G** (mobile H)

    Emmanuel Nicolas


    Dft rationalization2

    DFT Rationalization

    ω-B97X-D // Def2-TZVP (Pt) // 6-31G* (P/C/H) // 6-311+G** (mobile H)

    Emmanuel Nicolas


    Dft rationalization3

    DFT Rationalization

    ω-B97X-D // Def2-TZVP (Pt) // 6-31G* (P/C/H) // 6-311+G** (mobile H)

    Emmanuel Nicolas


    Conclusion

    Conclusion

    A stable Pt(II) complex, source of Pt(0) at room temperature has been synthesized.

    Chemistry at Pt(0) and Pt(II) is possible with this complex

    Furtherstudiesconcerningretrieval of Pt(0) from Pt hydride dimer are underway

    Emmanuel Nicolas


    Acknowledgments

    Acknowledgments

    PhD Advisor:

    Dr. Nicolas Mézailles

    GC/MS Studies:

    Dr. Stéphane Bouchonnet (DCMR)

    X-Ray Structures:

    Dr. Xavier Le Goff

    Dr. Louis Ricard

    Funding:

    PhoSciNet

    CNRS

    Ecole Polytechnique (fellowship)

    N. Mézailles has an open Ph.D. position for a non-French student within the SusPhos program.

    Emmanuel Nicolas


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