1 / 17

Marc DEVILLARD Under the supervision of Dr. G. Bouhadir and Dr. D. Bourissou

P E (E = B, Al)- Based Ambiphilic Compounds: Intramolecular Donor - Acceptor Interaction and Coordination Chemistry. Marc DEVILLARD Under the supervision of Dr. G. Bouhadir and Dr. D. Bourissou 10 th EWPC, Regensburg. Wednesday , March 20th 2013 .

kerry
Download Presentation

Marc DEVILLARD Under the supervision of Dr. G. Bouhadir and Dr. D. Bourissou

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  1. PE (E = B, Al)-BasedAmbiphilic Compounds: IntramolecularDonor-Acceptor Interaction and Coordination Chemistry Marc DEVILLARD Under the supervision of Dr. G. Bouhadir and Dr. D. Bourissou 10th EWPC, Regensburg Wednesday, March 20th 2013

  2. Our approach : P-(naphthyl)-B • LB : • >stronglydonating LA : easilytunable >sterics >electronics Kilian et al.Angew. Chem. Int. Ed.2012, 11, 1593 Ishikawa et al.Organometallics1992,51, 10150 • Linker : • >holdLB and LA in close proximity • >to whichextentcanit support LBLA? Sasamori, Tokitohet al.Angew. Chem. Int. Ed.2011, 50, 10940

  3. Preparation of the PBs Twoconsecutivehalogen/lithium exchange, electrophilictrappingsequences. 58 % 56 % 52 %

  4. Geometric and spectroscopic data C1 C3 C2 An interaction isobserved, evenwith B(Mes)2.

  5. Theoreticalstudies • Natural Bond Orbital (NBO) analysis[1] • sPBfoundat the first order : 30-40 % B, 60-70 % P • Natural Pop. Analysis (NPA) % B in sPB acidity of B ↗ ↘ E(2pB) B(Mes)2 B(Cy)2 Boraf. ↗ overlap Bader, R. F. W. Chem. Rev. 1991, 91, 893-928

  6. Theoreticalstudies • Atoms in Molecules (AIM) analysis[2] • Electron densitymaps: existence of a bond critical point (BCP) • 2r(r) > 0 and H(r) > 0 • open-shell interaction in the three cases • important covalent character of the bond P B [2]Bader, R. F. W. Chem. Rev. 1991, 91, 893-928

  7. Conclusion • Rare examples of naphthyl bridged phosphine-boranes, analyzed by spectroscopic, structural and computational methods[3] • Linker, a dual platform • Enforce the LBLA even for the bulky B(Mes)2 • Rigid but flexible enough to respond to LBLA • 31P NMR, 11B NMR, SaB, d(PB), NBO, AIM, the same trend • Existence of a bond • Covalent character increase with the acidity of B • Charges increase on each fragment with acidity of B [3]Inorg. Chem., in press

  8. Coordination of phosphine-alanes on transition metal LA : > stericallyprotected > acidicenough[4,5]? LB : > donating > NMR probe for coord. Fontaine et al. Organometallics2007, 26, 3807 Linker : > Csp2-Al bond > vinylic H : NMR probe? Organometallics2007, 27, 1675 [4]Appelt, C.; Slootweg, J. C.; Lammertsma, K.; Uhl, W. Angew. Chem. Int. Ed. 2013, 52, 1 [5]Appelt, C.; Slootweg, J. C.; Lammertsma, K.; Uhl, W. Angew. Chem. Int. Ed. 2012, 51, 5911

  9. Whatkind of behaviourcanweexpect? Al atom as a Z-type ligand

  10. Rh(I) and Pd(II) [Rh(nbd)Cl]2 31P {1H} d = 27.9 (d, 1JPRh = 145.8 Hz) 1H dvinylic = 7.66 (d, 3JHP = 36.4 Hz) 31P {1H} d = -14.2 1H dvinylic = 7.37 (d, 3JHP = 17.7 Hz) [Pd(allyl)Cl]2 31P {1H} d = 11.6 1H dvinylic = 7.67 (d, 3JHP = 38.6 Hz)

  11. Comparisonwith PB relatedsystems Same type of behaviour but Al is a muchstrongeracid.

  12. Conclusion and perspectives • This P/Al based FLP is a good candidate to study coordination on TM: thanks to itsrigidity (Csp2 linker) thanks to the greatacidity of the Al thanks to Hvinylic convenient NMR probe

  13. And after? • Get insight into new coordination modes Al atom as a Z-type ligand • Studies Pt(0) are in progress…

  14. Thanks to Toulouse, LHFA, LBPB group X-Rays diffraction analyses: S. Ladeira Institut de Chimie de Toulouse Quantum chemicalcalculations: Dr. K. Miqueu Université de Pau, France Muenster, Institut fürAnorganischeundAnalytischechemie Pr. W. Uhl Dr. C. Appelt J. Backs Amsterdam, Department of Chemistry and Pharmaceutical sciences Dr. C. Slootweg Dr. D. Bourissou Dr. G. Bouhadir

  15. Coordination to gold (I) 2 + [Au(SMe2)Cl] 31P NMR spectrum

  16. Coordination to gold (I) No contact between Cl and Au Al stronglypyrimidalyzedSaAl = 346.1° [Au(PMe3)Cl] 31P {1H} d = -3.3 (d, 2JPP = 327.9 Hz) 30.8 (d, 2JPP = 327.9 Hz) Indeed, the aluminumcancreate a free vacant site for the incoming phosphine.

More Related