Presentation is loading. Please wait.

Presentation is loading. Please wait.

Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium by Anthony G. M. Barrett, Mark R. Crimmin, Michael S.

Similar presentations


Presentation on theme: "Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium by Anthony G. M. Barrett, Mark R. Crimmin, Michael S."— Presentation transcript:

1 Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium by Anthony G. M. Barrett, Mark R. Crimmin, Michael S. Hill, and Panayiotis A. Procopiou Proceedings A Volume ():rspa20090558 January 25, 2010 ©2010 by The Royal Society

2 (a) Fundamental reactions of trivalent lanthanide organometallics: (i) σ-bond metathesis and (ii) insertion of unsaturated substrates into M–X2 σ-bonds. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

3 The Schlenk equilibrium of heavier Group II complexes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

4 Selected examples of well-defined, kinetically stabilized, heteroleptic heavier Group II complexes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

5 Calcium-mediated stereocontrolled polymerization of rac-lactide. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

6 Reaction scope of calcium and magnesium mediated intramolecular hydroamination of aminoalkenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

7 Diastereoselectivity in the intramolecular hydroamination of pro-chiral aminoalkenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

8 (a) Reaction of pre-catalysts 1 and 2 with primary amines. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

9 Proposed mechanism of Group II mediated hydroamination of aminoalkenes with (a) non- reversible and (b) reversible pre-catalyst generation. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

10 Aminotroponate, aminotropiniminate, bis(imidazolin-2-ylidene-1-yl)borate, tris (imi- dazolin-2- ylidene-1-yl)borate and triazenide supported Group II pre-catalysts for intramolecular hydroamination. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

11 Scope of hydroamination catalysis with complexes 3–9 and 11–12. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

12 Side-by-side comparison of reaction conditions for the intramolecular cyclization of 1-amino-2,2- diphenyl-4-pentene. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

13 Intermolecular hydroamination mediated by Group II complexes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

14 Proposed transition states to C–N bond formation in the anti-Markovnikov hydroamination of styrenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

15 Free energy profiles for the reaction of ethylene with ammonia catalysed by [{HNC(Me)CHC(Me)NH}M(NH2)]. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

16 Electron density difference maps for the alkene insertion (a) transition state and (b) intermediate for the Mg-mediated cycle. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

17 Insertion of 1,3-dialkyl carbodiimides into the Ca–N bonds of derivatives of 1. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

18 Scope of Group II mediated hydroamination of carbodiimides. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

19 (a) Proposed mechanism of the Group II mediated hydroamination of carbodiimides and (b) ORTEP representation of 13 thermal ellipsoids at 40% probability; H atoms are omitted for clarity. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

20 Group II catalysed addition of diphenylamine to isocyanates. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

21 (a) Proposed mechanism of the Group II catalysed addition of diphenylamine to isocyanates. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

22 Scope of alkene and alkyne hydrophosphination mediated by 1. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

23 Explanation for the observed regiochemistry in the Group II mediated hydrophos- phination of styrenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

24 (a) Proposed mechanism of the hydrophosphination of diphenylacetylene catalysed by 1 and (b) ORTEP representation of 15 thermal ellipsoids at 20% probability; H atoms are omitted for clarity. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

25 Hydrophosphination of diphenylacetylene and 1,4-diphenylbutadiyne catalysed by [Ca{PPh2}2(THF)4]. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

26 Group II mediated hydrophosphination of carbodiimides. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

27 (a) Proposed mechanism of Group II mediated hydrophosphination of carbodiimides. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

28 Scope of Group II mediated hydrosilylation of alkenes and dienes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

29 Reaction of 1 with PhSiH3 to yield the molecular hydride 17. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

30 Proposed mechanisms of the Group II mediated hydrosilylation of alkenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

31 Group II catalysed hydrosilylation of ketones. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

32 Reaction scope of the calcium-mediated hydrogenation of activated alkenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society

33 (a) Proposed mechanism for the Group II mediated hydrogenation of alkenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi:10.1098/rspa.2009.0558 ©2010 by The Royal Society


Download ppt "Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium by Anthony G. M. Barrett, Mark R. Crimmin, Michael S."

Similar presentations


Ads by Google