Gold Coordination Complexes
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294–2968C (decomp); UV/Vis (CH2Cl2):
l
(e)=373 nm (3.81ꢄ
Cy3PAuCl. The resulting suspension was stirred at room temperature
overnight. The solvent was removed by rotary evaporation. The residue
was extracted with CH2Cl2 and filtered through a layer of Celite. The sol-
vent was then removed by rotary evaporation, and the resulting solid was
triturated with pentane. Diffusion of pentane into a saturated CHCl3 so-
lution yielded orange crystals. The crystals were washed with pentane
and dried under vacuum as the pure product. Yield: 0.1193 g, 96%;
1H NMR (CDCl3): d=7.81 (s, 2H), 7.76 (d, J=16.4 Hz, 2H), 7.41–7.45
(m, 4H), 7.11 (d, J=16.0 Hz, 2H), 7.14 (d, J=16.4 Hz, 2H), 1.50–
2.02 ppm (m, 132H); 31P{H} NMR (400 MHz, CDCl3): d=56.852 (s),
56.742 ppm (s); MS (MALDI): m/z calcd: 2284.03 [M]+; found: 2284.7;
elemental analysis calcd (%) for C102H146Au4P4: C 53.64, H 6.44; found:
C 53.38, H 6.19; UV/Vis (CH2Cl2): l (e)=282 (3.37ꢄ104), 333 (6.94ꢄ
104), 389 nm (4.85ꢄ104 mꢀ1 cmꢀ1) ; emission (CH2Cl2 ex. 389 nm): l=447,
468 nm.
104 mꢀ1 cmꢀ1); emission (CH2Cl2, ex. 373 nm): l=414, 437, 463 nm.
These materials were pure by an NMR criterion and used without further
purification.
(E)-1-[(Cy3P)Au]-4-(4-tert-butylstyryl)benzene
(1):
[(Cy3P)AuBr]
(0.0923 g, 0.166 mmol), L1 (0.0900 g, 0.25 mmol), Cs2CO3 (0.1619 g,
0.50 mmol) were suspended in isopropyl alcohol (10 mL) and charged
into a round bottom flask. After degassing, the reaction vessel was im-
mersed in a 508C oil bath, and stirred under Ar for 24 h. After cooling,
isopropyl alcohol was removed under rotary evaporation, and the re-
maining solid was extracted into benzene (50 mL) and filtered through
Celite. The solution was put under a rotary evaporator and benzene was
removed. The residue was triturated with pentane. Vacuum filtration
gave the product as a white powder. The white powder was then dis-
solved in a minimum amount of benzene and filtered through Celite. Dif-
fusing pentane into the concentrated benzene solution afforded the prod-
uct as colorless crystals. Yield: 0.1000 g, 85%; 1H NMR (C6D6): d=8.13–
8.17 (m, 2H), 7.69 (d, J=7.6 Hz, 2H), 7.40 (d, J=8 Hz, 2H), 7.20–7.27
(m, 4H); 1.34–1.85 (m, 24H, (C6H11)3), 1.24 (s, 9H, tert-butyl), 1.00–
1.05 ppm (m, 9H, (C6H11)3); 31P{1H} NMR (C6D6): d=57.5 ppm; HR-MS
(ES+): m/z calcd: 713.3550 [M+H]+; found: 713.3632; elemental analysis
calcd (%) for C36H52AuP: C 60.67, H 7.35; found: C 60.41, H 7.31; UV/
1,4-Bis(4-[(Cy3P)Au]styryl)benzene
(5):
[(Cy3P)AuBr]
(0.0743 g,
0.133 mmol), L3 (0.0392 g, 0.071 mmol), and Cs2CO3 (0.0956 g,
0.29 mmol) were suspended in isopropyl alcohol (10 mL) and charged
into a round bottom flask. Benzene (5 mL) was then added to promote
dissolution of the starting materials. After degassing, the reaction vessel
was immersed in a 458C oil bath, and stirred under Ar for 24 h. After
cooling, the solvents were removed under rotary evaporation, and the re-
maining solid was extracted into dichloromethane (100 mL) and filtered
through Celite. Solvent was removed by rotary evaporation. The residue
was triturated with pentane. Vacuum filtration gave the product as
a yellow powder. The yellow powder was then dissolved in a minimum
amount of dichloromethane and filtered through Celite. Diffusing ether
into the concentrated dichloromethane solution afforded the product as
yellow crystals. Yield: 0.050 g, 61%; 1H NMR (CDCl3): d=7.49–7.53 (m,
4H), 7.46 (s, 3H), 7.42 (d, J=6.8 Hz, 4H), 7.37 (d, J=0.8 Hz, 1H), 7.06
Vis (2-MeTHF):
emission (2-MeTHF, ex. 325 nm): l=357, 374 nm.
1,4-Bis[(Cy3P)Au]-2,5-bis(4-tert-butylstyryl)benzene (2): [(Cy3P)AuBr]
l
(e)=288 (3.65ꢄ104), 330 nm (3.95ꢄ104 mꢀ1 cmꢀ1);
ACHTUNGTRENNUNG
(0.0794 g, 0.142 mmol), L2 (0.0506 g, 0.076 mmol), Cs2CO3 (0.1022 g,
0.31 mmol) were suspended in isopropyl alcohol (10 mL) and charged
into a round bottom flask. Benzene (5 mL) was then added to promote
dissolution of the starting materials. After degassing, the reaction vessel
was immersed in a 458C oil bath, and stirred under Ar for 24 h. After
cooling, the solvents were removed under rotary evaporation, and the re-
maining solid was extracted into dichloromethane (100 mL) and filtered
through Celite. The solution was evaporated to dryness. The residue was
triturated with pentane. Vacuum filtration gave the product as a yellow
powder. The yellow powder was then dissolved in a minimum amount of
dichloromethane and filtered through Celite. Diffusing ether into the
concentrated dichloromethane solution afforded the product as yellow
crystals. Yield: 0.0640 g, 67%; 1H NMR (CDCl3): d=7.89–7.91 (m, 2H),
7.78 (d, J=16.0 Hz, 2H), 7.44 (d, J=8.4 Hz, 4H), 7.29 (d, J=8.4 Hz,
(dd, J=24.4, 16.8 Hz, 2H), 1.52–2.06 ppm (m, 66H; 2ACTHNUTRGNEUNG
(C6H11)3); 31P{1H}
NMR (CDCl3): d=57.9 ppm; HR-MS (ES+): m/z calcd: 1235.5439 [M+
H]+; found: 1235.5647; elemental analysis calcd (%) for C58H82Au2P2: C
56.40, H 6.69; found: C 56.66, H 6.59; UV/Vis (CH2Cl2): l (e)=373 nm
(1.32ꢄ104 mꢀ1 cmꢀ1); emission (CH2Cl2 ex. 373 nm): l=389, 411 nm.
2,5-Bis(4-
[(Cy3P)Au]benzaldehyde (0.0890 g, 0.133 mmol) and tetraethyl[(2,5-di-
bromo-1,4-phenylene)bis(methylene)]bis(phosphonate) (0.0410 g,
A
(6):
4-
0.076 mmol) were dissolved in THF (20 mL). The solution was degassed,
and NaH (0.0040 g, 0.17 mmol) was added. The mixture was then re-
fluxed for 4 h. After cooling to RT, ice was added to the reaction mixture
under vigorous stirring. The yellow precipitate generated was collected
by vacuum filtration, washed with THF and water several times, and
dried in the air. The resulting yellow powder was then redissolved in
methylene chloride and washed with water three times. The methylene
chloride layer was collected and dried over MgSO4. The solvent was then
removed under rotary evaporation. A yellow powder was collected after
trituration with pentane. Yield: 0.050 g, 61%; 1H NMR (CDCl3): d=7.85
(s, 2H), 7.51–7.54 (m, 4H), 7.44 (d, J=6.8 Hz, 4H), 7.29 (d, J=16.0 Hz,
4H), 7.14 (d, J=16.0 Hz, 2H), 1.55–2.08 (m, 66H; 2ACTHNUGTRNE(UNG C6H11)3), 1.32 ppm
(s, 18H, tert-butyl); 31P{1H} NMR (CDCl3): d=57.9 ppm; HR-MS (ES+):
m/z calcd: 1348.6587 [M+H]+; found: 1348.6978; elemental analysis
calcd (%) for C66H98Au2P2: C 58.83, H 7.33; found: C 58.72, H 7.19; UV/
Vis (CH2Cl2): l (e)=297 (1.85ꢄ104), 380 nm (3.13ꢄ104 mꢀ1 cmꢀ1); emis-
sion (CH2Cl2 ex. 380 nm): l=425 nm.
2,5-Bis(4-tert-butylstyryl)-1,4-bis
N
(3):
[(Cy3P)AuCl] (85.2 mg, 0.166 mmol) was suspended in methanol (5 mL).
KOtBu (17.1 mg, 0.153 mmol) and 1,4-diethynyl-2,5-bis(4-tert-butylstyr-
yl)benzene (36.4 mg, 0.082 mmol) were combined in methanol (5 mL),
and the mixture was then added to the suspension of Cy3PAuCl. The re-
sulting suspension was stirred at room temperature overnight. The sol-
vent was removed by rotary evaporation. The residue was extracted with
CH2Cl2 and filtered through a layer of Celite. CH2Cl2 was then removed
by rotary evaporation, and the resulting solid was triturated with pen-
tane. Diffusing pentane into a saturated CHCl3 solution yielded a yellow
powder, which was washed with pentane and dried under vacuum. Yield:
0.0681 g, 60%; 1H NMR (CDCl3): d=7.83 (s, 2H), 7.78 (d, J=16.4 Hz,
2H), 7.51 (d, J=8.4 Hz, 4H), 7.34 (d, J=8.8 Hz, 4H), 7.14 (d, J=
16.4 Hz, 2H), 1.43–2.05 ppm (m, 66H); 31P{H} NMR (400 MHz, CDCl3)
d=56.8 ppm (s); MS (ES+): m/z calcd: 1395.6475 [M+Na]+; found,
1395.7225; elemental analysis calcd (%) for C70H98Au2P2: C 60.25, H
7.08; found: C 59.97, H 6.80; UV/Vis (CH2Cl2): l (e)=324 (4.53ꢄ104),
371 nm (2.35ꢄ104 mꢀ1 cmꢀ1); emission (CH2Cl2 ex. 371 nm): l=427 nm.
2H), 7.01 (d, J=16.0 Hz, 2H), 1.52–2.07 ppm (m, 66H;
2ACHTUNGTRENNUNG(C6H11)3);
31P{1H} NMR (CDCl3): d=57.6 ppm; HR-MS (ES+): m/z calcd:
1393.3512 [M+H]+; found: 1393.4550; UV/Vis (CH2Cl2): l (e)=375 nm
(2.51ꢄ104 mꢀ1 cmꢀ1); emission (CH2Cl2 ex. 375 nm): l=403, 429, 455 nm.
2,5-Bis(4-
[(Cy3P)Au]-4-ethynylbenzene (0.1288 g, 0.212 mmol) and tetraethyl[(2,5-
dibromo-1,4-phenylene)bis(methylene)]bis(phosphonate) (0.0683 g,
A
(7):
1-
0.127 mmol) were dissolved in THF (20 mL). The solution was degassed,
and NaH (0.0061 g, 0.255 mmol) was added. The mixture was then re-
fluxed for 4 h. After cooling to RT, ice was added to the reaction mixture
under vigorous stirring. The yellow precipitate generated was collected
by vacuum filtration, washed with THF and water several times, and
dried in the air. The dried powder was then redissolved in methylene
chloride, and washed with water twice. The methylene chloride layer was
collected and dried over MgSO4. The solvent was then removed under
rotary evaporation. A yellow powder was collected after trituration with
pentane. Yield: 0.0837 g, 55%; 1H NMR (CDCl3): d=7.84 (s, 2H), 7.50
(d, J=8.4 Hz, 4H), 7.42(d, J=8.4 Hz, 4H), 7.32 (d, J=16.0 Hz, 2H), 7.00
2,5-Bis(4-
(4): [(Cy3P)AuCl] (113.4 mg, 0.221 mmol) was suspended in methanol
(5 mL). 1,4-Diethynyl-2,5-bis(4-ethynylstyryl)benzene (20.4 mg,
ACHTUNGTRENNUNG[(Cy3P)Au]ethynylstyryl)-1,4-bisACHTUGNTREN(NUNG [(Cy3P)Au]ethynyl)benzene
0.054 mmol) and KOtBu (24.2 mg, 0.216 mmol) were also combined in
MeOH (5 mL), and the mixture was then added to the suspension of
(d, J=16.4 Hz, 2H), 1.52–2.07 ppm (m, 66H; 2AHCTUNGTRENNNUG
Chem. Eur. J. 2012, 18, 6316 – 6327
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6325