1 / 15

Novel Aspects in the coordination chemistry of the P 4 Q 3 (Q = S, Se) cage

Novel Aspects in the coordination chemistry of the P 4 Q 3 (Q = S, Se) cage. Andreas Biegerl , Joachim Wachter, Manfred Zabel 5th EWPC 2008. Introduction Ligand behavior of P 4 S 3 towards W(CO) 5 fragments Coordination polymers from Cu (I) halides and P 4 Q 3 (Q = S, Se)

huy
Download Presentation

Novel Aspects in the coordination chemistry of the P 4 Q 3 (Q = S, Se) cage

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. NovelAspects in thecoordinationchemistryofthe P4Q3 (Q = S, Se) cage Andreas Biegerl, Joachim Wachter, Manfred Zabel 5th EWPC 2008

  2. Introduction • Ligand behaviorof P4S3towards W(CO)5fragments • CoordinationpolymersfromCu(I) halidesand P4Q3 (Q = S, Se) • Crystallographicand31P MAS NMR investigations • Conclusions

  3. 1. Coordinationpossibilitiesof P4Q3 (Q = S, Se) 7 examples for apical P coordination (1974–2007) 2 examplesfor basal P coordination[(triphos)Re(CO)2(P4Q3)]+ (Q = S, Se), Peruzzini, 2002 1 exampleforsimultaneous apical and basal P coordination[{CpRu(PPh3)2}2(P4Q3)]+ (Q = S, Se), Peruzzini, 2007 1 examplefor P and S coordination[Ag(P4S3)2][WCA], Krossing, 2002 • Polymeric compounds in the solid-state • Depolymerisation in CH2Cl2

  4. 2. Ligand behavior of the P4S3 cage towards W(CO)5 fragments (n = 1 – 4)

  5. 3. CoordinationpolymersfromCuXand P/Q (Q = S, Se) cagemolecules 1977: First hintsfortheformationofpolymers Reactionof P4S3andCuX (X = Cl, Br, I) dissolved in organicsolvents W. F. Ibáñez, M. G. González, C. E. Clavijo, Z. Anorg. Allg. Chem. 1977,432, 253. 1999: Solid-state syntheses • High temperature reaction of CuI, P, and S • (CuI)3(b-P4S4) • CuCl and CuBr not suitable for reaction A. Pfitzner, S. Reiser, Inorg. Chem. 1999,38, 2451. Ouridea: EmploythesolubilityofbothP4Q3andCuXfortheconstructionofsupramolecularpolymersbyinterdiffusiontechniques

  6. Demonstration ofthediffusionexperiment P4Q3in CH2Cl23 to6 mmol·L-1 CuHal in CH3CN9 to28 mmol·L-1

  7. The system P4S3/CuCl c(CuCl) = 18 mmol L-1V(CH3CN) = 20 mL c(CuCl) = 9 mmol L-1 V(CH3CN) = 10 mL SelectivesynthesesbychangingtheconcentrationofCuCl

  8. Crystal structure of 3D-(P4S3)2(CuCl)3 (section)

  9. Section of the crystal structure of 2D-(P4Se3)(CuCl)

  10. 3D crystalstructureof (P4S3)3(CuCl)7 (section)

  11. Crystal structure of 1D-(P4Q3)(CuI) (Q = S, Se)

  12. 31P MAS NMR spectroscopy of (P4S3)(CuI) P1 P2 P3/3a

  13. Raman spectra of P4S3 and (P4S3)(CuI)

  14. 4. Conclusions • First examplesforinorganiccoordinationpolymers (quaternaryphases) fromsolution • All P-coordinationof P4S3 in molecularandpolymericstructures • First examplesforcoordinationpolymersof P4Se3 • Future Objectives: • Vibrationalspectroscopyand DFT calculations

  15. Thanks to • Help andpatience: Dr. J. Wachter • 31P MAS NMR spectra: Prof. Dr. E. Brunner, C. GrögerRaman spectra: B. Schwanitz • Financial support: • Prof. Dr. M. Scheer andDeutsche Forschungsgemeinschaft

More Related