Gábor Balázs University of Regensburg ICOMC 2010 Dr. Max Mustermann Referat Kommunikation & Marketing Verwaltung Gábor Balázs Institute of Inorganic Chemistry University of Regensburg COMPLEXES WITH TERMINALLY COORDINATED EQ (E = P, As; Q = S, Se, Te) LIGANDS

Gábor Balázs University of Regensburg ICOMC 2010 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

Gábor Balázs University of Regensburg ICOMC 2010 EQ E = P, As, Sb, Bi Q = O, S, Se, Te Coordination modes of NO

Gábor Balázs University of Regensburg ICOMC 2010 Possible synthetic roots for complexes with η 1 -EQ ligands

Gábor Balázs University of Regensburg ICOMC 2010 O. J. Scherer, J. Braun, P. Walther, G. Heckmann, G. Wolmershaeuser, Angew. Chem., 103, 1991, 861. O. J. Scherer, C. Vondung, G. Wolmershauser, Angew. Chem. Int. Ed. Engl., 36, 1997, O. J. Scherer, S. Weigel, G. Wolmershauser, Heteroat. Chem., 10, 1999, 622. J. F. Corrigan, S. Doherty, N. J. Taylor and A. J. Carty, J. Am. Chem. Soc., 116, 1994, J. E. Davies, M. J. Mays, E. J. Pook, P. R. Raithby, P. K. Tompkin, Chem. Commun., 1997, C. E. Laplaza, W. M. Davis, C. C. Cummins Angew. Chem. Int. Ed. Engl. 1995, 34, M. J. A. Johnson, A. L. Odom, C. C. Cummins Chem. Commun., 1997, Carty Mays Scherer Cummins

Gábor Balázs University of Regensburg ICOMC 2010 Complexes with Terminal Phosphido, Arsido and Antimonido Ligands SchrockCumminsScheer R. R. Schrock, N. C. Zanetti, W. N. Davis Angew. Chem. Int. Ed. Engl. 1995, 34, C. E. Laplaza, W. M. Davis, C. C. Cummins Angew. Chem. Int. Ed. Engl. 1995, 34, M. Scheer, K. Schuster, T. A. Budzichowski, M. H. Chisholm, W. E. Streib Chem. Commun. 1995, 1671.

Gábor Balázs University of Regensburg ICOMC 2010 R. R. Schrock, N. C. Zanetti, W. N. Davis Angew. Chem. Int. Ed. Engl. 1995, 34, M. Scheer, J. Müller, M. Häser Angew. Chem. 1996, 108, 2637.

Gábor Balázs University of Regensburg ICOMC 2010 M. Scheer, J. Müller, G. Baum, M. Häser Chem. Commun. 1998, M. Scheer, J. Müller, M. Schiffer, G. Baum, R. Winter Chem. Eur. J. 2000, 6, W-Sb 2.574(1) Å

Gábor Balázs University of Regensburg ICOMC C NMR δ = ppm (W≡C) W(1)-C(19) 1.813(1)Å

Gábor Balázs University of Regensburg ICOMC 2010 G. Balázs, M. Sierka, M. Scheer Angew. Chem. Int. Ed. 2005, 44, 4920.

Gábor Balázs University of Regensburg ICOMC 2010 Bond lengths (Å) and Angles (°): Exp. Calc. W – Sb2.525(2) W – N eq 1.994(8) W – N ax 2.33(1) N eq – W – Sb101.8(2) N ax – W – Sb180.0 –

Gábor Balázs University of Regensburg ICOMC 2010

Gábor Balázs University of Regensburg ICOMC 2010 W–P 2.142(1) Å 31 P NMR: δ = -188 ppm 31 P NMR: δ = 1239 ppm W–As 2.258(1) Å

Gábor Balázs University of Regensburg ICOMC 2010 W–P 2.544(3) Å W–I (9) Å P–I 2.729(3) and 2.795(3) Å

Gábor Balázs University of Regensburg ICOMC 2010 G. Balázs, J. C. Green, M. Scheer Chem. Eur. J. 2006, 12, G. Balázs, J. C. Green, D. M. P. Mingos Eur. J. Inorg. Chem. 2007, P NMR: δ = ppm; 1 J PW = Hz 31 P NMR: δ = ppm; 1 J PW = 138 Hz Terminally Coordinated EQ Complexes

Gábor Balázs University of Regensburg ICOMC 2010

Gábor Balázs University of Regensburg ICOMC P{ 1 H} NMR 1 J PSe = 790 Hz 1 J PW = 727 Hz 1 J PTe = 1759 Hz 1 J PW = 649 Hz

Gábor Balázs University of Regensburg ICOMC P{ 1 H} NMR

Gábor Balázs University of Regensburg ICOMC 2010 DFT Optimized (RI-DFT, BP86, SV(P)) Transition State Structure

Gábor Balázs University of Regensburg ICOMC 2010

Gábor Balázs University of Regensburg ICOMC 2010 PAs SSeTeS W–E2.158(1)2.152(1)2.159(1)2.256(1) E–QE–Q1.940(2)2.081(1)2.294(1)2.048(2) W–E–Q177.1(4)177.3(1)176.6(1)177.6(1) N ax –W–E178.0(4)178.3(1)177.8(1)178.7(2) Selected bond lengths (Å) and angles (°) (N 3 N)W ≡ E W–P 2.162(4) W–As 2.290(1)

Gábor Balázs University of Regensburg ICOMC 2010 Single Marks

Gábor Balázs University of Regensburg ICOMC 2010 PAsSbBi −482−429−333−293 σ W-E-Q Hybrid. E = P sp 0.5 E = Bi sp 0.7 σ W-E Hybrid. E = P sp 3.3 E = Bi sp 6.6 QPAsSbBi O−415−341−259−204 S−401−339−262−207 Se−400−339−259−205 Te−401−340−261−208 W–E Bond Dissociation Energies (kJ·mol −1 )

Gábor Balázs University of Regensburg ICOMC 2010 OSSeTe P As Sb Bi E–Q Bond Dissociation Energies (kJ·mol −1 ) PAsSbBi O−415−341−259−204 S−401−339−262−207 Se−400−339−259−205 Te−401−340−261−208 W–E Bond Dissociation Energies (kJ·mol −1 )

Gábor Balázs University of Regensburg ICOMC 2010 Molecular Orbital Interaction Diagram

Gábor Balázs University of Regensburg ICOMC 2010 Molecular Orbital Interaction Diagram

Gábor Balázs University of Regensburg ICOMC 2010 Comparative MO Diagram in Complexes N 3 NW(PQ)

Gábor Balázs University of Regensburg ICOMC 2010 QEW–EE–Q OP As Sb Bi SP As Sb Bi SeP As Sb Bi TeP As Sb Bi P = ♦, As = ■, Sb = ▲, Bi = ● Hirshfeld Charge Distribution: Positive on W and Negative on Q Fractional Bond Orders

Gábor Balázs University of Regensburg ICOMC 2010 Reactivity of N 3 NW(PTe)

Gábor Balázs University of Regensburg ICOMC 2010 Reactivity of N 3 NW(PTe)

Gábor Balázs University of Regensburg ICOMC 2010 Conclusions Synthesis of complexes containing linearly coordinated EQ ligands of the heavier group 15 and 16 Elements is possible The [(N 3 N)W(PTe) complex can readily be used as a tellurium transfer reagent The π system can be best described as two orthogonal three centered two electron system

Gábor Balázs University of Regensburg ICOMC 2010 Acknowledgment Prof. Dr. M. Scheer Prof. Dr. J. C. Green Prof. Dr. D. M. P. Mingos Alexander von Humboldt Foundation Deutsche Forschungsgemeinschaft University of Regensburg Thank you for your attention