COMPLEXES WITH TERMINALLY COORDINATED EQ (E = P, As; Q = S, Se, Te) LIGANDS

1. COMPLEXES WITH TERMINALLY COORDINATED EQ (E = P, As; Q = S, Se, Te) LIGANDS

2. Contents • Introduction • Complexes with W≡E (E = group 15 element) triple bonds • Synthesis of complexes with linearly coordinated EQ ligands (Q = group 16 element) • Reactivity of linearly coordinated EQ Complexes • Summary

3. Coordination modes of NO EQ E = P, As, Sb, Bi Q = O, S, Se, Te

4. Possible synthetic roots for complexes with η1-EQ ligands

5. Complexes with Terminal Phosphido, Arsido and AntimonidoLigands Schrock Cummins Scheer R. R. Schrock, N. C. Zanetti, W. N. Davis Angew. Chem. Int. Ed. Engl.1995, 34, 2044. C. E. Laplaza, W. M. Davis, C. C. CumminsAngew. Chem. Int. Ed. Engl.1995, 34, 2042. M. Scheer, K. Schuster, T. A. Budzichowski, M. H. Chisholm, W. E. StreibChem. Commun.1995, 1671.

6. 31P NMR: δ = 1080 ppm R. R. Schrock, N. C. Zanetti, W. N. Davis Angew. Chem. Int. Ed. Engl.1995, 34, 2044. M. Scheer, J. Müller, M. HäserAngew. Chem.1996, 108, 2637.

7. W-Sb 2.574(1) Å M. Scheer, J. Müller, G. Baum, M. HäserChem. Commun.1998, 2505. M. Scheer, J. Müller, M. Schiffer, G. Baum, R. Winter Chem. Eur. J.2000, 6, 1252.

8. 13C NMR δ = 319.4 ppm (W≡C) W(1)-C(19) 1.813(1)Å

9. G. Balázs, M. Sierka, M. Scheer Angew. Chem. Int. Ed.2005, 44, 4920.

10. Bond lengths (Å) andAngles (°): Exp. Calc. W – Sb 2.525(2) 2.514 W – Neq 1.994(8) 2.015 W – Nax 2.33(1) 2.516 Neq – W – Sb 101.8(2) 104.1 Nax – W – Sb 180.0 –

12. 31P NMR: δ = 1239 ppm 31P NMR: δ = -188 ppm W–P 2.142(1) Å [(HIPT)N3NW≡As] W–As 2.258(1) Å

13. W–P 2.544(3) Å W–I 2.7434(9) Å P–I 2.729(3) and 2.795(3) Å

14. Terminally Coordinated EQ Complexes 31P NMR: δ = 1080.3 ppm; 1JPW = 138 Hz 31P NMR: δ = 342.3 ppm; 1JPW = 771.5 Hz G. Balázs, J. C. Green, M. ScheerChem. Eur. J.2006, 12, 8603. G. Balázs, J. C. Green, D. M. P. MingosEur. J. Inorg. Chem.2007, 2443. C. E. Laplaza, W. M. Davis, C. C. CumminsAngew. Chem. Int. Ed. Engl.1995, 34, 2042. M. J. A. Johnson, A. L. Odom, C. C. Cummins Chem. Commun., 1997, 1523. Cummins

16. 31P{1H} NMR 1JPTe = 1759 Hz 1JPW = 649 Hz 1JPSe = 790 Hz 1JPW = 727 Hz

17. 31P{1H} NMR

18. DFT Optimized (RI-DFT, BP86, SV(P)) Transition State Structure

20. Selected bond lengths (Å) and angles (°) (N3N)W ≡ E W–P 2.162(4) W–As 2.290(1)

21. single marks

22. W–E Bond Dissociation Energies (kJ·mol−1) σ W-E-Q Hybrid. E = P sp0.5 E = Bi sp0.7 W–E Bond Dissociation Energies (kJ·mol−1) σ W-E Hybrid. E = P sp3.3 E = Bi sp6.6

23. W–E Bond Dissociation Energies (kJ·mol−1) E–QBond Dissociation Energies (kJ·mol−1)

24. Molecular Orbital Interaction Diagram

25. Molecular Orbital Interaction Diagram

26. Hirshfeld Charge Distribution: Positive on W and Negative on Q Fractional Bond Orders P = ♦,As = ■, Sb = ▲, Bi = ●

27. Reactivity of N3NW(PTe)

28. Reactivity of N3NW(PTe)

29. Conclusions • Synthesis of complexes containing linearly coordinated EQ ligands of the heavier group 15 and 16 Elements is possible • The π system can be best described as two orthogonal three centered two electron system • The [(N3N)W(PTe)] complex can readily be used as a tellurium transfer reagent

30. Acknowledgment • Prof. Dr. M. Scheer • Prof. Dr. J. C. Green • Prof. Dr. D. M. P. Mingos Thank you for your attention • Alexander von Humboldt Foundation • Deutsche Forschungsgemeinschaft • University of Regensburg