supplementary material · web viewjoanna grundy, martyn p. coles*, anthony g. avent and peter b....

Supplementary material (ESI) for Chem. Commun.This journal is © The Royal Society of Chemistry 2004

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:

[email protected]; Tel: +44 (0)1273 877339; Fax: +44 (0)1273 677196

Contents:

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

%. 1H NMR (C6D6, 298 K): δ 8.36-8.30 (m, 2H, o-C6H5), 8.00-7.94 (m, 2H, o-C6H5), 7.07-

6.88 (m, 6.4H, NH and m- and p-C6H5), 5.52 (s, 0.6H, NH), 4.07 (m, 0.5H, N(amino)-CH), 3.87

(m, 0.5H, N(imino)-CH), 3.64 (m, 0.5H, N(imino)-CH), 3.42 (m, 0.5H, N(amino)-CH), 1.94-0.86 (m,

20H, Cy). 13C NMR (C6D6, 298 K) 147.5 (d, 1JPC = 132 Hz, PCN2), 144.0 (d, 1JPC = 52 Hz,

PCN2), 133.8 (d, 1JPC = 70 Hz, i-C6H5), 133.2 (d, 1JPC = 57 Hz, i-C6H5), 132.9 (d, 2JPC = 10 Hz,

o-C6H5), 132.2 (d, 2JPC = 11 Hz, o-C6H5), 131.7 (d, 3JPC = 3 Hz, m-C6H5), 131.2 (d, 3JPC = 3 Hz,

m-C6H5), 128.4 (d, 4JPC = 12 Hz, p-C6H5), 127.7 (d, 4JPC = 3 Hz, p-C6H5), 58.5, (d, 3JPC = 24 Hz,

C-Cy), 57.4 (d, 3JPC = 8 Hz, C-Cy), 53.8 (d, 3JPC = 22 Hz, C-Cy), 50.2 (C-Cy), 34.8 (Cy),

34.5 (Cy), 34.2 (Cy), 32.1 (Cy), 26.3 (Cy), 26.2 (Cy), 26.1 (Cy), 25.5 (Cy), 24.8 (Cy), 24.6

(Cy). 31P NMR (C6D6, 298 K) δ 38.6, 34.1. IR (Nujol mull, cm-1): 3320s (N-H), 1614m

(C=N), 1259w, 1100m, 997w, 976w, 887w, 800w, 709m, 644m. MS (EI, m/z): 424 [M+],

392 [M+ -S], 218 [M+ - C(NCy)2H], 207 [M+ - P(S)Ph2].

Preparation of Ph2P(S)C{NiPr}{NHiPr} (3)

Compound 3 was prepared using the procedure outlined for compound 4 using the following

quantities: Sulfur (0.032 g, 1.00 mmol) in toluene (20 mL) Ph2PC{NiPr}{NHiPr} (1, 0.31 g,

1.00 mmol) in toluene (20 mL) yielding 0.24 g (72 %).

Anal. Calc. for C19H25N2PS: C, 66.25; H, 7.31, N, 8.13 %. Found: C, 66.00; H, 7.22; N, 7.80

%. 1H NMR (C6D6, 298 K): δ 8.34-7.89 (m, 4H, o-C6H5), 7.06-6.95 (m, 6H, m- and p- C6H5),

6.79 (br dd, 0.4H, 3JPH = 8 Hz, NH), 5.23 (br s, 0.6H, NH), 4.23 (br m, 1H, NCH), 3.81 (m,

0.5H, NCH), 3.57 (m, 0.5H, NCH), 1.28-0.81 (m, 12H, CH3). 13C NMR (C6D6, 298 K): δ

147.7 (d, 1JPC = 132 Hz, PCN2), 144.0 (d, 1JPC = 54 Hz, PCN2), 133.6 (d, 1JPC = 48 Hz, i-C6H5),

132.9 (d, 2JPC = 10 Hz, o-C6H5), 132.6 (d, 2JPC = 39 Hz, i-C6H5) 132.0 (d, 2JPC = 12 Hz, o-

C6H5), 131.5 (d, 3JPC = 4 Hz, m-C6H5), 131.1 (d, 3JPC = 3 Hz, m-C6H5), 128.8 (d, 4JPC = 12 Hz,

p-C6H5), 128.0 (d, 4JPC = 12 Hz, p-C6H5), 50.5 (d, 3JPC = 16 Hz, CMe2), 49.0 (d, 3JPC = 21 Hz,

CMe2), 46.5 (d, 3JPC = 9 Hz, CMe2), 43.5 (d, 3JPC = 5 Hz, CMe2), 24.2 (CH3), 24.1 (CH3), 23.5

2

(CH3), 21.8 (CH3). 31P NMR (C6D6, 298 K): δ 38.6, 34.1. IR (Nujol mull, cm-1): 3426s (N-

H), 1611m (C=N), 1353s, 1311w, 1228m, 1174m, 1158m, 1117m, 1094m, 1027w, 997w,

976w, 837w, 801w, 723m, 709m, 648m.

Preparation of Ph2P(Se)C{NCy}{NHCy} (6)

To a solution of Ph2PC{NCy}{NHCy} (2, 0.5 g, 1.27 mmol) in toluene (50 mL) was added

grey selenium (0.1 g, 1.27 mmol) and allowed to stir for 8 hrs. This resulted in a colourless

solution. Removal of volatiles and recrystallisation from a slowly cooled solution in heptane

gave colourless crystals of Ph2P(Se)C(NCy)(NHCy). Yield 0.39 g (65 %).

Anal. Calc. for C25H33N2PSe: C, 63.69; H, 7.05; N, 5.94 %; Found C, 63.61; H, 7.22;N, 5.74

%. 1H NMR (C6D6, 298 K): δ 8.30-8.23 (m, 1.7H, o-C6H5), 8.02-7.95 (m, 2.3H, o-C6H5),

7.09- 6.96 (m, 6.4H, NH and m- and p-C6H5), 5.59 (s, 0.6H, NH), 4.06 (m, 0.5 H, N(amino)-CH),

3.85 (m, N(imino)-CH), 3.65 (m, 0.5 H, N(imino)-CH), 3.45 (m, 0.5 H, N(amino)-CH), 1.94-0.88 (m,

20H, Cy). 13C NMR (C7D8, 298 K) 145.6 (d, 1JPC = 123.4 Hz, PCN2), 141.3 (d, 1JPC = 42.8 Hz,

PCN2), 132.7 (d, 1JPC = 76.6 Hz, i-C6H5), 132.5 (d, 1JPC = 67.6 Hz, i-C6H5), 133.2 (d, 2JPC = 10

Hz, o-C6H5), 132.6 (d, 2JPC = 11 Hz, o-C6H5), 131.6 (d, 3JPC = 3 Hz, m-C6H5), 131.0 (d, 3JPC = 3

Hz, m-C6H5), 128.7 (d, 4JPC = 12 Hz, p-C6H5), 127.8 (d, 4JPC = 12 Hz, p-C6H5), 58.4, (d, 3JPC =

15 Hz, C-Cy), 57.4 (d, 3JPC = 18 Hz, C-Cy), 53.8 (d, 3JPC = 10 Hz, C-Cy), 50.3 (d,3JPC = 6

Hz, C-Cy), 34.4 (Cy), 34.0 (Cy), 32.1 (Cy), 26.2 (Cy), 26.1 (Cy), 25.5 (Cy), 24.42 (Cy). 31P

NMR (C6D6, 298 K): δ 36.0 (1JSeP = 721 Hz), 24.3 (1JSeP = 752 Hz). 77Se NMR (C7D8, 298

K): δ -223.6 (d, 1JSeP = 752 Hz), -310.9 (d, 1JSeP = 721 Hz). IR (Nujol mull, cm-1): 3298m (N-

H), 1614s (C=N), 1257w, 1185w, 1099s, 1025w, 996m, 887m, 743m, 698m. MS (EI, m/z):

472 [M+], 392 [M+ -Se], 265 [M+ - C(NCy)2H], 207 [M+ - P(Se)Ph2].

Preparation of Ph2P(Se)C{NiPr}{NHiPr} (5)

Compound 5 was prepared using the procedure outlined for compound 6 using the following

quantities: Grey selenium (0.078 g, 1 mmol) in toluene (20 mL), Ph2PC{NiPr}{NHiPr} (1,

0.31 g, 1 mmol) in toluene (20 mL), yield 0.29 g (74 %).

Anal. Calc. for C19H25N2PSe: C, 58.31; H, 6.43, N, 7.15 %. Found: C, 51.22; H, 5.36; N, 6.02

%.* 1H NMR (C6D6, 298 K): δ 8.28-7.91 (m, 4H, o-C6H5), 7.03-6.92 (m, 6.3H, NH, m- and

p- C6H5), 5.43 (br, 0.7H NH), 4.19 (br m, 1H, NCH), 3.81 (m, 0.5H, NCH), 3.59 (m, 0.5H,

NCH), 1.23-0.79 (m, 12H, CH3). 13C NMR (C7D8, 298 K): δ 145.9 (d, 1JPC = 123 Hz, PCN2),

141.6 (d, 1JPC = 43 Hz, PCN2), 133.2 (d, 2JPC = 10 Hz, o-C6H5), 132.5 (d, 1JPC = 77 Hz, i-* Despite repeated attempts, elemental analysis failed to give accurate results, believed to be due to residual unreacted selenium.

3

C6H5), 132.5 (d, 2JPC = 11 Hz, o-C6H5), 131.6 (d, 3JPC = 3 Hz, m-C6H5), 131.6 (d, 3JPC = 3 Hz,

m-C6H5), 131.4 (d, 2JPC = 68 Hz, i-C6H5) 128.7 (d, 4JPC = 12 Hz, p-C6H5), 127.8 (d, 4JPC = 13

Hz, p-C6H5), 50.5 (d, 3JPC = 16 Hz, CMe2), 49.3 (d, 3JPC = 21 Hz, CMe2), 46.8 (d, 3JPC = 9 Hz,

CMe2), 43.8 (d, 3JPC = 5 Hz, CMe2), 24.2 (CH3), 24.1 (CH3), 23.6 (CH3), 21.9 (CH3). 31P

NMR (C6H6, 298 K): δ 35.8 (1JPSe = 721 Hz), 23.8 (1JPSe = 755 Hz). 77Se NMR (C7D8, 298

K): δ –222.3 (d, 1JPSe = 755 Hz), -304 (1JPSe = 721 Hz). IR (Nujol mull, cm-1): 3321s (N-H),

1614m (C=N), 1353s, 1149m, 1101m, 887w, 799w, 721m, 709m, 644m.

4

Figure 1 1H NMR spectrum of compound 6 with peak labeling scheme (D8-toluene, 298 K, * = solvent peak).

Figure 2 31P{1H} NMR spectrum of compound 6 (C6D6 at 298 K).

5

Figure 3 77Se {1H} NMR spectrum of compound 6 (D8-toluene, 298 K).

Figure 4 Proton coupled 77Se NMR spectra of compound 6, with selective decoupling of NH proton at 6.96 (298 K, D8 toluene).

6

Figure 5 Irradiation of NH peak at 5.4 ppm revealing second NH peak at 6.9 ppm (298 K, D8 toluene).

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0

C D

Figure 6 Selective decoupling of NH protons (298 K, D8 toluene).

7

Figure 7 Proton coupled 13C NMR spectra, with selective decoupling of N(imino) α-cyclohexyl protons (298 K, D8 toluene).

8


Figure 8 Variable temperature 1H NMR spectra of 6 (500 MHz, D8-toluene, 198 - 298K, low field region).

9


Table 1 Variable temperature NMR data for 6 (500 MHz, D8-toluene, 198 - 298 K)

T 1/T Keq ln Keq198 0.00505 0.398 -0.92208 0.00481 0.398 -0.92218 0.00459 0.408 -0.90228 0.00439 0.418 -0.87248 0.00403 0.395 -0.93258 0.00388 0.478 -0.74278 0.0036 0.720 -0.33298 0.00356 0.734 -0.31

Figure 9

10

Figue 10

11


Figure 11 Infra red spectrum (CDCl3) of 6 (NH stretching region).

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Figure 12 Infra red spectrum (CDCl3) of 6 (CN stretching region).

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supplementary material · web viewjoanna grundy, martyn p. coles*, anthony g. avent and peter b....

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