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Organometallic P n -Ligand Complexes as Supramolecular Building Blocks

Organometallic P n -Ligand Complexes as Supramolecular Building Blocks. Laurence J. Gregoriades Institute of Inorganic Chemistry (Research Group of Prof. Manfred Scheer) University of Regensburg. Outline. 1: Introduction 2: [CpMo(CO) 2 ( h 3 -P 3 )] ( 2a )

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Organometallic P n -Ligand Complexes as Supramolecular Building Blocks

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  1. Organometallic Pn-Ligand Complexes as Supramolecular Building Blocks Laurence J. Gregoriades Institute of Inorganic Chemistry (Research Group of Prof. Manfred Scheer) University of Regensburg

  2. Outline 1: Introduction 2: [CpMo(CO)2(h3-P3)] (2a) 3: [Cp*Mo(CO)2(h3-P3)] (2b) 4: [Cp*Mo(CO)2(h3-As3)] (2c) 5: [Cp*Fe(h5-P5)] (4) 6: [(Cp*Mo)2(h6-P6)] (5) 7: Summary

  3. 1: Introduction Organometallic Pn-Ligand Complexes asSupramolecularBuilding Blocks Organometallic Pn-Ligand Complexes as Supramolecular Building Blocks

  4. Supramolecular Chemistry Involves the use of weak, non-covalent interactions for the synthesis of highly ordered oligomeric and polymeric aggregates. Examples of such interactions: hydrogen bonding van der Waals forces Coulombic interactions dipole-dipole interactions dative bonding interactions 

  5. Pn-Ligand Complexes 1 2a: Cpx = Cp 2b: Cpx = Cp* 3 4 6 5 1-5 Scherer et al.; 6 Ellis et al.

  6. 2: [CpMo(CO)2(h3-P3)] (2a)

  7. P–P 2.134(3)-2.203(3) Å; P–P (free ligand) 2.126(2)-2.141(2) Å Molecular mass (osmometric, CH2Cl2): 2440 ± 122 g/mol Calculated for [Ag{CpMo(CO)2P3}2][Al{OC(CF3)3}4]: 1695 g/mol ESI-MS (CH2Cl2): m/z (%) = 728.6 (100) [Ag{CpMo(CO)2P3}2]+

  8. –140 °C –120 °C –110 °C –100 °C –80 °C –60 °C 27 °C -220 -260 -300 -340 -380 -420 -460 (ppm) Solution 31P-NMR (CD2Cl2/THF d8 (1:3))

  9. -133 °C * * * * -100 -200 -400 -500 -600 -700 -300 0 (ppm) Solid State 31P MAS-NMR (Measured by Dipl.-Phys. C. Gröger) RT ♦ * *  = spinning side-bands ♦ = impurity 0 -100 -200 -400 -500 -600 -700 -300 (ppm)

  10. ESI-MS (CH2Cl2): m/z (%) = 1038.6 (17) [Ag{CpMo(CO)2P3}3]+ 31P-NMR (CD2Cl2/THF d8 (1:3), 27 °C):  (ppm) = -359.0 (singlet) (CD2Cl2/THF d8 (1:3), -120 °C):  (ppm) = -396.2 (broad), -293.7 (broad) (integration ratio 2:1) (solid state MAS, RT):  (ppm) = -350.7 (broad) Molecular mass (osmometric, CH2Cl2): 1916 ± 96 g/mol Calculated for [Ag{CpMo(CO)2P3}3][Al{OC(CF3)3}4]: 2005 g/mol

  11. 3: [Cp*Mo(CO)2(h3-P3)] (2b)

  12. ESI-MS (CH2Cl2): m/z (%) = 866.9 (100) [Ag{Cp*Mo(CO)2P3}3]+ Molecular mass (osmometric, CH2Cl2): 1953 ± 98 g/mol Calculated for [Ag{CpMo(CO)2P3}3][Al{OC(CF3)3}4]: 1835 g/mol

  13. –120 °C –100 °C Solution 31P-NMR (CD2Cl2/THF d8 (1:3)) –80 °C 27 °C -220 -260 -300 -340 -380 -420 -460 (ppm) Solid State 31P MAS-NMR (Measured by Dipl-Phys. C. Gröger) RT -100 -200 -400 -500 -600 -700 -300 0 (ppm)

  14. X = Cl, Br

  15. 4: [Cp*Mo(CO)2(h3-As3)] (2c)

  16. As–As 2.368(2)-2.528(2) Å As–As (free ligand) 2.372(1)-2.377(2) Å ESI-MS (CH2Cl2): m/z (%) = 1130.7 (100) [Ag{Cp*Mo(CO)2As3}2]+ Molecular mass (osmometric, CH2Cl2): 2756 ± 138 g/mol Calculated for [Ag{Cp*Mo(CO)2As3}2][Al{OC(CF3)3}4]: 2099 g/mol

  17. Enthalpy of formation of the dication in CH2Cl2: -19 kJ/mol (25 °C) Dr. Marek Sierka, Humboldt University, Berlin

  18. 5: [Cp*Fe(h5-P5)] (4)

  19. =

  20. ESI-MS (CH2Cl2): m/z (%) = 798.8 (100) [Ag(Cp*FeP5)2]+ P–P 2.107(5)-2.156(4) Å P–P (free ligand) 2.116(2)-2.127(2) Å 31P-NMR (CD2Cl2, 27 °C):  (ppm) = 154.2 (singlet) (CD2Cl2, -90 °C):  (ppm) = 123.2 (broad), 150.9 (broad) (integration ratio  1:1) Molecular mass (osmometric, CH2Cl2): 1725 ± 86 g/mol Calculated for [Ag(Cp*FeP5)2][Al{OC(CF3)3}4]: 1767 g/mol

  21. Enthalpy of formation of the dication in CH2Cl2: -2 kJ/mol (25 °C) -12 kJ/mol (-90 °C) Prof. Ingo Krossing, EPFL, Lausanne (TURBOMOLE, COSMO/BP86/SV(P))

  22. 6: [(Cp*Mo)2(h6-P6)] (5)

  23. 7: Summary • [CpMo(CO)2(h3-P3)] (2a) and [Cp*Mo(CO)2(h3-P3)] (2b) • new oligomers and polymers • structural design by stoichiometric control • effect of exchanging Cp for Cp* demonstrated • dynamic behaviour in solution and in the solid state • [Cp*Mo(CO)2(h3-As3)] (2c) • first aggregate based on Asn-ligand complex • effect of exchanging P for As in complex 2b demonstrated • dynamic behaviour in solution • [Cp*Fe(h5-P5)] (4) • novel 1D polymer • cyclo-P5 moieties in a h1:h2 (1,2,3) coordination mode • dynamic behaviour in solution • [(Cp*Mo)2(h6-P6)] (5) • first supramolecular aggregate containing complex 5 • corrugated 2D polymer

  24. Acknowledgements • Prof. Manfred Scheer and colleagues • Prof. Henri Brunner and colleagues • Prof. Ingo Krossing and colleagues (Lausanne) • Prof. Hellmut Eckert and colleagues (Münster) • Prof. Eike Brunner and Dipl-Phys. Christian Gröger • Dr. Marek Sierka (Berlin) • NeRo Graphic Design • Helen, Gregory and Rebekah Gregoriades and the Neumann family • Universities of Karlsruhe and Regensburg • German Research Foundation (DFG)

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