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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)

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

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  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

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