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Synthesis of [2]- and [3]- ferrocenophanes containing trivalent phosphorus centers

Synthesis of [2]- and [3]- ferrocenophanes containing trivalent phosphorus centers. Denis Kargin Chemische Hybridmaterialien Prof. Dr. Rudolf Pietschnig. Ferrocenophanes. Rinehart Jr. et al . 1960. Osborne et al . 1975.

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Synthesis of [2]- and [3]- ferrocenophanes containing trivalent phosphorus centers

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  1. Synthesis of [2]- and [3]-ferrocenophanes containing trivalent phosphorus centers Denis Kargin Chemische Hybridmaterialien Prof. Dr. Rudolf Pietschnig

  2. Ferrocenophanes Rinehart Jr. et al. 1960 Osborne et al. 1975 I. Manners et al., Angew. Chem. Int. Ed.2007, 46, 5060 – 5081.

  3. Bridged diphosphanes Mizuta et al. 2002 Hey-Hawkins et al. 2011 Glueck et al. 2012 Pietschnig et al. 2009 Mizuta et al. 2012 Allcock et al. 1983 Allcock,et al, J. Am. Chem. Soc. 1988, 110, 980. C. Moser, F. Belaj, R. Pietschnig, Chem. Eur. J. 2009, 15, 12589 – 12591. T. Mizuta et al., J. Organomet. Chem. 2012, 713, 80. Diploma thesis, Cornelia Ratzenhofer, 2012. T. Mizuta et al., Angew. Chem. Int. Ed. 2002,41, 3897 – 3898. A.Kreienbrink, E. Hey-Hawkins et al., Angew. Chem. Int. Ed. 2011, 50, 4701 – 4703. Glueck et al., Org. Lett. 2012, 14, 4238 – 4241.

  4. Synthetical approaches

  5. Introducing organic moieties (R= tBu, Ph, Mes)

  6. Introducing organic moieties (R= tBu, Ph, Mes) T. Mizuta, J. Organomet. Chem. 2012, 713, 80.

  7. Towards bisphosphano-[2]ferrocenophanes triclinic P -1 R1 = 0.0421 (R= tBu, Ph, Mes)

  8. Electrochemistry E1/2 (1)= 25 mV E1/2 (2)= 168 mV Diploma thesis, Cornelia Ratzenhofer, 2012.

  9. Electrochemistry Square wave voltammogram vs FcH / FcH+ Cyclovoltammogram vs FcH / FcH+

  10. gauche anti Linear Oligophosphanes • prone to disproportionation • stabilized by incorporation into cyclic backbone or steric protection gauche-effect Stephan et al., Angew. Chem. Int. Ed.2001, 40, 1865 – 1867. Hey-Hawkins et al., Inorganic Chemistry 2006, 45, 9107 − 9113.

  11. P-H addition to P=P RRRS-Configuration 24 = 16 isomers first bis-1,3-dihydrotriphosphane! Tbt= orthorhombic P212121 (chiral) R1: 0.0558 Flack parameter: -0.01(2) C. Moser, M. Nieger, R. Pietschnig, Organometallics2006, 15, 25, 2667.

  12. Hydrolytic P-P connection 4 asymmetric centers  24 = 16 isomers possible restraint  23 = 8 isomers (4 pair of enantiomers) C. Moser, F. Belaj, R. Pietschnig, Chem. Eur. J. 2009, 15, 12589 – 12591.

  13. Geometric parameters D. Herbert, U. Mayer, I. Manners , Angew. Chem. Int. Ed.2007, 46, 5060 – 5081.

  14.  = 34.7° 1 = 13.8° 2 = 14.8° Oxydihydrotetraphosphane • = 11.5° orthorhombic P212121 (chiral) R1: 0.0355 Flack parameter: 0.00(3) C. Moser, F. Belaj, R. Pietschnig, Chem. Eur. J. 2009, 15, 12589 – 12591.

  15. experimental spectrum [ppm] simulated spectrum [ppm] To [3]-ferrocenophanes from Bisdiphosphenes Slow dimerisation (months) 1,3-Dimer C. Moser, F. Belaj, R. Pietschnig, Chem. Eur. J. 2009, 15, 12589 – 12591.

  16. NPN-[3]ferrocenophanes X triclinic P 1 R1 = 0.0654

  17. NPN-[3]ferrocenophanes • = 11.4° 1 = 2.8° 2 = 0.1°

  18. To other dinuclear [3]ferrocenophanes JP-Si: 88 Hz (R= tBu, Ph, Mes)

  19. Summary and Outlook • synthetic access to [2]-diphosphaferrocenophanes • interaction between Fc and diphosphane units?? • H-terminated oligophosphanes • via addition P-H to P=P • via addition of H2O to 2 P=P • synthetic access to dinuclear [3]-ferrocenophanes (P/N or P/Si) • interaction between Fc and bridging units?? • access to ferrocene based silylenes??

  20. Acknowledgements Alumni: Carmen Moser Andreas Orthaber Cornelia Ratzenhofer ForSupportingtheelectrochemicalmeasurements: Thomas Ebert Lin Wu For x-raydiffractionanalysisanddiscussion Ferdinand Belaj Clemens Bruhn Christian Färber € € €:

  21. PD a) experimental 53 % 14 % b) simulated 21 % 12 % Isomer I Isomer II Isomer III Isomer IV all Isomers 31P-NMR Spectra PA PB PC C. Moser, F. Belaj, R. Pietschnig, Chem. Eur. J. 2009, 15, 12589 – 12591.

  22. 31P NMR exp. vs. sim. exp. sim. (31P{1H} NMR, deut. Toluene, 360 MHz)

  23. 1,1’ Ferrocenylene Bisdiphosphenes 31P-NMR:

  24. Isomer II RRSS / SSRR g. – a. – a. 14 % Isomer III SRSR / RSRS a. – a. – g. 21 % Isomer IV SRSS / RSRR a. – a. – a. 12 % Isomer I RRSR / SSRS g. – a. – g. 53 % Relative abundance of isomers

  25. NPN-[3]Ferrocenophane N1-P1.724(5) Å N2-P1.734(5) Å CCp-N1-P-CTbt -61.6(5)° CCp-N2-P-CTbt 57.4(5)° CTbt-PC-PD-CTbt 164.2(5)° Si1-N1-P-CTbt 129.2(3)° Si2-N2-P-CTbt -147.9(3)° triclinic P 1 (Nr. 2) R1 = 0.0654

  26. Oxydihydrotetraphosphane Crystal structure: PA-PB 2.217(14) Å PB-PD 2.279(8) Å PA-PC 2.170(10) Å PA-O 1.494(6) Å PD-PA-PB-PC -93.5(4)° CFc-PA-PB-CFc 45.9(5)° CTbt-PC-PD-CTbt 164.2(5)° orthorhombic P212121 (No 19) (chiral) R1: 0.0355 Flack parameter: 0.00(3) Lit

  27. O-H addition to P=P Addition of H2O:

  28. Inversion barriere on trivalent phosphor Acyclic phosphines • Increase: • Decrease: • Electronwithdrawingsubsti- • tuents in paraposition • Conjugative effects Inversion barrier: 29 – 36 kcal/mol Diphosphines • Increase: • Ringstrain • Electronegativesubstituents • Substituentsbearinglonepairs • Decrease: • Bulkygroups • Conjugative effects Baechler, R. D.; Mislow, K. J. Am. Chem. Soc. 1970, 92, 3090–3093. J. Lambert, G. Jackson, D. Mueller. J. Am. Chem. Soc. 1970, 92, 3093–3097

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