SUPPLEMENTARY MATERIAL · Web viewJoanna Grundy, Martyn P. Coles*, Anthony G. Avent and Peter B. Hitchcock Department of Chemistry, University of Sussex, Falmer, Brighton BN1 9QJ,
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Self-organisation in P-substituted guanidines leading to solution-state isomerisation†
Joanna Grundy, Martyn P. Coles*, Anthony G. Avent and Peter B. HitchcockDepartment of Chemistry, University of Sussex, Falmer, Brighton BN1 9QJ, UK. E-mail:
2 Preparation of Ph2P(S)C{NCy}{NHCy} (4).2 Preparation of Ph2P(S)C{NiPr}{NHiPr} (3).3 Preparation of Ph2P(Se)C{NCy}{NHCy} (6)3 Preparation of Ph2P(Se)C{NiPr}{NHiPr} (5).5 Figure 1 1H NMR spectrum of compound 6 with peak labeling scheme (D8-
toluene, 298 K, * = solvent peak).5 Figure 2 31P{1H} NMR spectrum of compound 6 (C6D6 at 298 K).6 Figure 3 77Se {1H} NMR spectrum of compound 6 (D8-toluene, 298 K).6 Figure 4 Proton coupled 77Se NMR spectra of compound 6, with selective
decoupling of NH proton at 6.96 (298 K, D8 toluene).7 Figure 5 Irradiation of NH peak at 5.4 ppm revealing second NH peak at 6.9
ppm (298 K, D8 toluene).7 Figure 6 Selective decoupling of NH protons (298 K, D8-toluene).8 Figure 7 Proton coupled 13C NMR spectra, with selective decoupling of N(imino)
α-cyclohexyl protons (298 K, D8 toluene).9 Figure 8 Variable temperature 1H NMR spectra of 6 (500 MHz, D8-toluene, 198
- 298 K, low field region).10 Table 1 Variable temperature NMR data for 6 (500 MHz, D8-toluene, 198 - 298
K).10 Figure 9 van't Hoff plot 198 - 298 K.10 Figure 10 van't Hoff plot 248 - 298 K.11 Figure 11 Infra red spectrum (CDCl3) of 6 (NH stretching region).12 Figure 12 Infra red spectrum (CDCl3) of 6 (CN stretching region).
1
Preparation of Ph2P(S)C{NCy}{NHCy} (4)
A suspension of sulfur (0.04 g, 1.20 mmol) in toluene (20 mL) was added dropwise at room
temperature to a solution of Ph2PC{NCy}{NHCy} (2, 0.47 g, 1.20 mmol) in toluene (20 mL)
and allowed to stir for 8 hrs. Volatiles were removed in vacuo resulting in an off white oil.
Crystallisation by slow cooling of a hot heptane solution gives colourless crystals of
Ph2P(S)C{NCy}{NHCy}. Yield 0.48 g (95 %).
Anal. Calc. for C25H33N2PS: C, 70.92; H, 7.83, N, 6.60 %. Found: C, 70.95; H, 7.91; N, 6.55