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Matthew Ray Supervisor: Dr. Petr Kilian

Divergent Behaviour of Phosphino-Phosphoniums; Quasi-Phosphoniums or Phosphine Stabilised Phospheniums?. Matthew Ray Supervisor: Dr. Petr Kilian. p eri -Substitution. P. Kilian , D. Philp , A. M. Z. Slawin and J. D. Woollins, Eur. J. Inorg . Chem. , 2003, 249 .

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Matthew Ray Supervisor: Dr. Petr Kilian

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  1. Divergent Behaviour of Phosphino-Phosphoniums; Quasi-Phosphoniums or Phosphine Stabilised Phospheniums? Matthew Ray Supervisor: Dr.PetrKilian

  2. peri-Substitution P. Kilian, D. Philp, A. M. Z. Slawin and J. D. Woollins, Eur. J. Inorg. Chem., 2003, 249. P. Wawrzyniak, A. L. Fuller, A. M. Z. Slawin and P. Kilian, Inorg. Chem., 2009, 48, 2500.

  3. Reaction with Dichlorophosphines R = NMe2 31P{1H}NMR: δ36.2 (d), 66.2 (d). 1JPP= 412 Hz δ -36.2 (d), 54.6 (d). 1JPP = 311 Hz P-P = 2.25 Å 31P{1H} NMR: δ -34.5 (d), 60.0 (d). 1JPP = 303 Hz P-P = 2.23 Å

  4. Reaction with iPrPCl2 31P{1H} NMR: δ -22.9 (d), 60.6 (d). 1JPP = 306 Hz

  5. Geminally Bis(peri-substituted) Tridentate Phosphine • Peri-distances both 3.2 Å • Outer P atoms 4.4 Å apart • Room temperature 31P{1H} NMR broad

  6. Tridentate Phosphine 31P{1H} NMR C1 B1 A2 B2 A1 C2 Sim 223 K 353 K RT a) RTb) 353 K:AB2 pattern (A = -1.82 , B = -8.12 ppm ; JAB = 140 Hz) c) 223 K: Two ABC patterns in ratio of 58:42 d) Simulation: Two ABC spin systems in 3:2 ratio (A1 = -4.53 , B1 = -1.52, C1 -15.59 ,A2 = -11.87, B2 = -10.88, C2 -17.14 ppm; JA1-B1 = 93.9 , JB1-C1 = 142.3 , JB1-C1 = 0 , ; JA2-B2 = 139.7 , JB1‑C1 = 137.6 , JB1-C1 = 7.3 Hz)

  7. Phosphino-Phosphoniums J. J. Weigand, S. D. Riegel, N. Burfordand A. Decken, J. Am. Chem. Soc., 2007, 129, 7969.

  8. Synthesis of 1,2-Diphosphoniums 31P{1H} NMR: R = Phδ 31.0 (d), 52.8 (d). 1JPP = 27.6 Hz R = Fc δ 33.2 (d), 45.9 (d). 1JPP = 45.3 Hz

  9. Phosphino-phosphonium Reduction R = Ph 31P{1H} NMR: δ -40.0 (d), -12.3 (d). 4JPP = 169 Hz 31P NMR: δ -40.0 (dd, 1JPH = 203 Hz), -12.3 (d). 4JPP = 169 Hz R = Fc 31P{1H} NMR: δ -51.9 (d), -9.3 (d). 4JPP = 199 Hz 31P NMR: δ-51.9 (dd, 1JPH = 236 Hz), -9.4 (d). 4JPP = 199 Hz P-P = 3.05 Å

  10. Phosphino-phosphonium Reduction P-P = 3.61 Å 31P{1H} NMR: δ -6.6 (br s), 39.4 (br s) 31P NMR: δ -6.6 (d, 1JPH= 376.1 Hz), 39.5 (br s) 11B NMR : δ -39.3 (br s)

  11. Phosphino-phosphonium Co-ordination Chemistry 31P{1H} NMR: δ 36.0 (d), 52.3 (d). 1JPP = 250.4 Hz P-P = 2.27 Å

  12. Phosphino-phosphonium Co-ordination Chemistry P-P = 3.26 Å 31P{1H} NMR: δ 12.8 (d, 1JPPt= 3201 Hz), 41.9 (d, 1JPPt = 3836 Hz ). 2JPP = 26.4 Hz

  13. Phosphino-phosphonium Co-ordination Chemistry P-P = 3.24 Å 31P{1H} NMR: δ 11.3 (d, 1JPPt = 3409 Hz), 38.5 (d, 1JPPt = 3582 Hz). 2JPP= 28.0 Hz

  14. Phosphino-phosphonium Co-ordination Chemistry 31P{1H} NMR: AA'XX' spin system (A/A' = iPr2P, X/X' = PhP) δ 14.7 (m, A/A'), -176.6 (m, X/X'). trans-2JAX = 322 Hz, cis-2JAX = 140 Hz, JXX' = 4.6 Hz, 4JAA' = 2.2 Hz) P-P = 3.29 Å

  15. Conclusions

  16. Conclusions

  17. Acknowledgements Dr.PetrKilian • Prof. Alex Slawin, KasunArachchige • Caroline Horsburgh • Dr. Tomas Lebl • Kilian/Woollins/Slawin Group

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