Gold(I) Macrocycles and [2]Catenanes Containing Sulfone-Functionalised Diacetylide Ligands
FULL PAPER
Table 5. The hinge angles and aryl twist angles [°] for selected complexes
Hinge group X
Spacer group Y
Hinge angle
Aryl twists
Structure
SO2
SO2
SO2
SO2
S
CH2
CMe2
CC
104.7(3)
109.4(7)
105.9(4)
105.4(5)/ 107.9(5)
104.3(3)
115.0(6)/115.3(5)
111.2(7)/111.9(9)
100, 100
ring
ring
ring
catenane
ring
catenane
catenane
Fe(C5H4)2
(CH2)5
(CH2)3
(CH2)4
(CH2)4
(CH2)4
97(95), 87(43)[a]
95, 65
89, 69/87, 71[b]
97, 1
92, 33/93, 29
[b]
[b]
52, 47/49, 39
[a]
[b]
Two values because of structural disorder. Two values for two independent rings.
3 h to produce a yellow precipitate. The solid was then collected by
filtration, washed with THF, MeOH, Et2O and pentane, and dried.
Yield: 0.499 g, 91%. The product was insoluble in common organic
solvents. IR (nujol): ν˜ ϭ 1996 cmϪ1 (w) (CϵC). C18H12Au2O4S
(718.3): calcd. C 30.10, H 1.68; found C 30.56, H 1.92.
ences could be caused by subtle differences in hinge angles,
or by electronic effects of the hinge groups on the strengths
of phenylϪaryl attractions. Nevertheless, the comparison of
the hinge groups S and SO2 does show how the orientation
of the aryl groups can be controlled and the effect could in
principle be used to trigger catenation on oxidation of S to
SO2. Our attempts to demonstrate the effect directly have
been unsuccessful since the AuϪC bonds are not stable to
strongly oxidising conditions.
Macrocycle 3a:
A mixture of 2 (0.100 g, 0.139 mmol) and
Ph2PCCPPh2 (0.044 g, 0.112 mmol) in CH2Cl2 (10 mL) was stirred
for 3 h at room temperature. The mixture was filtered through Cel-
ite and the filtrate concentrated under vacuum (ca. 2Ϫ3 mL). Addi-
tion of Et2O precipitated an off-white solid. The powder was col-
lected by filtration, washed with Et2O and pentane, and dried.
Yield 0.078 g, 51%. 31P NMR (162 MHz, CDCl3, 25 °C): δ ϭ 18.59
ppm. 1H NMR (400 MHz, CDCl3, 25 °C): δ ϭ 7.86 (d, J ϭ 7.9 Hz,
4 H, C6H4), 7.62Ϫ7.69 (m, 8 H, Ph), 7.52Ϫ7.58 (m, 4 H, Ph),
7.43Ϫ7.49 (m, 8 H, Ph), 7.13 (d, J ϭ 9.3 Hz, 4 H, C6H4), 4.91 (s,
4 H, OCH2) ppm. MALDI-TOF MS: m/z (%) ϭ 1113 (19) [MH]ϩ.
C44H32Au2O4PS·1/2Et2O (1149.7): calcd. C 48.05, H 3.24; found C
48.86, H 2.92. Crystals suitable for X-ray diffraction were grown
by slow diffusion of hexane into a concentrated CH2Cl2 solution.
Experimental Section
General Remarks: NMR spectra were recorded using Varian Mer-
cury 400 and Inova 600 MHz spectrometers. 1H and 13C NMR
chemical shifts are reported relative to tetramethylsilane, while 31P
NMR chemical shifts are reported relative to 85% H3PO4 as an
external standard. IR spectra were recorded using a PerkinϪElmer
2000 FT-IR as Nujol mulls on NaCl plates. MALDI-TOF spectra
were recorded using a Micromass MALDI-LR instrument in posit-
ive ion mode. The samples were dissolved in CH2Cl2 and spotted
onto a dried layer of matrix [1 µL of α-cyano-4-hydroxycinnamic
acid (10 mg/mL in CAN/EtOH, 50:50)]. The samples were analysed
in reflection mode and mass spectra were externally calibrated us-
ing a tryptic digest of alcohol dehydrogenase. The complex [AuCl-
(SMe2)] was prepared by a literature procedure.[18] All other chem-
icals and solvents were from commercial sources and used as re-
ceived. All reactions involving gold complexes were carried out in
reactions vessels shielded from light. Elemental analyses were car-
ried out by Guelph Chemical Laboratories, Guelph, Canada.
Macrocycle 3b: This was prepared by the procedure described for
3a from 2 (0.075 g, 0.104 mmol) and [Fe(C5H4PPh2)2] (0.046 g,
0.083 mmol). The product was isolated as a pale-yellow solid. Yield
0.097 g, 74%. 31P NMR (162 MHz, CDCl3, 25 °C): δ ϭ 36.79 ppm.
1H NMR (400 MHz, CDCl3, 25 °C): δ ϭ 7.87 (d, J ϭ 8.6 Hz, 4
H, C6H4), 7.36Ϫ7.51 (m, 20 H, Ph), 7.16 (d, J ϭ 9.3 Hz, 4 H,
C6H4), 4.94 (s, 4 H, OCH2), 4.33 (s, 4 H, C5H4), 4.27 (s, 4 H, C5H4)
ppm. MALDI-TOF MS: m/z (%)
ϭ
1273 (100) [MH]ϩ.
C52H40Au2FeO4P2S·0.2CH2Cl2 (1289.7): calcd. C 48.50, H 3.15;
found C 48.54, H 3.18. Crystals suitable for X-ray diffraction were
grown by slow diffusion of Et2O into a concentrated nitrobenzene
solution.
Diacetylide Ligand 1: BrCH2CϵCH (2.4 g, 17.58 mmol) and
K2CO3 (1.6 g, 11.58 mmol) were added to a solution of O2S-
(4-C6H4OH)2 (2.0 g, 7.99 mmol) in acetone (50 mL). The mixture
was heated under reflux for about 24 h. The cooled solution was
filtered to give a pale yellow filtrate. The solvent was removed un-
der reduced pressure and the resultant off-white solid dried under
vacuum. Yield: 2.3 g, 88%. IR (nujol): ν˜ ϭ 2080 (br, w) 2129 cmϪ1
Macrocycle 3c: This was prepared by the procedure described for
3a from 2 (0.100 g, 0.139 mmol) and Ph2P(CH2)4PPh2 (0.113 g,
0.083 mmol). The product was isolated as a colourless solid. Yield
0.110 g, 71%. 31P NMR (162 MHz, CDCl3, 25 °C): δ ϭ 38.27 ppm.
1H NMR (400 MHz, CDCl3, 25 °C): δ ϭ 7.85 (d, J ϭ 8.6 Hz, 4
H, C6H4), 7.60Ϫ7.38 (m, 20 H, Ph), 7.15 (d, J ϭ 8.6 Hz, 4 H,
C6H4), 4.90 (s, 4 H, OCH2), 2.27 (m, 4 H, CH2), 1.65 (m, 4 H,
CH2) ppm. MALDI-TOF MS: m/z (%) ϭ 1144 (100) [MH]ϩ.
C46H40Au2O4P2S (1144.8): calcd. C 48.26, H 3.52; found C 48.16,
H 3.75.
1
(s) (CϵC). H NMR (400 MHz, [D6]acetone, 25 °C): δ ϭ 7.91 (d,
J ϭ 9.4 Hz, 4 H, C6H4), 7.16 (d, J ϭ 8.6 Hz, 4 H, C6H4), 4.89 (d,
J ϭ 2.4 Hz, 2 H, OCH2), 3.14 (t, J ϭ 2.4 Hz, 2 H, CϵH) ppm.
13C NMR (100 MHz, [D6]acetone, 25 °C): δ ϭ 161.2, 135.2, 129.6,
115.6 (all C6H4), 78.2 (CϵCH), 77.2 (CϵCH), 56.2 (OCH2) ppm.
MS: m/z (%) ϭ 326 (72) [M]ϩ. C18H14O4S (326.4): calcd. C 66.24,
H .32; found C 65.79, H 4.57.
Macrocycle 3d This was prepared by the procedure described for
3a from 2 (0.100 g, 0.139 mmol) and Ph2P(CH2)5PPh2 (0.052 g,
0.118 mmol). The product was isolated as a cream-coloured solid.
Yield 0.126 g, 80%. 31P NMR (162 MHz, CDCl3, 25 °C): δ ϭ 37.06
ppm. 1H NMR (400 MHz, CDCl3, 25 °C): δ ϭ 7.87 (d, J ϭ 8.6 Hz,
Digold(i) Diacetylide 2: [AuCl(SMe2)] (0.452 g, 1.53 mmol) was dis-
solved in THF (50 mL)/MeOH (30 mL). A solution of 1 (0.250 g,
0.77 mmol) and Et3N (0.4 mL, 2.87 mmol) in THF (20 mL)/MeOH 4 H, C6H4), 7.54Ϫ7.62 (m, 8 H, Ph), 7.39Ϫ7.51 (m, 12 H, Ph), 7.16
(10 mL) was added to this. The resulting mixture was stirred for
(d, J ϭ 8.6 Hz, 4 H, C6H4), 4.95 (s, 4 H, OCH2), 2.29 (m, 4 H,
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