66
E.C. Constable et al. / Polyhedron 27 (2008) 65–70
2.2. Compound 2
2.4. Compound 4
n
Compound 1 (0.219 g, 0.763 mmol), Bu3PAuCl (0.330
g, 0.759 mmol) and CuI (14.7 mg, 77.2 lmol) were added
to Et3N (10 ml). The reaction mixture was stirred at room
temperature for 4 h. Solvent was then removed and the
product was separated by column chromatography (alu-
mina, CH2Cl2–acetone 99:1). There was a single fraction,
from which 2 was isolated as a white oil (0.233 g,
0.340 mmol, 44.8%). Crystals of 2 could be obtained by
slow evaporation of the crude reaction mixture. Com-
pound 2: 1H NMR (400 MHz, CDCl3) d (ppm) 8.65
(ddd, J 4.7, 1.8, 0.8 Hz, 2H, HA6), 8.54 (dt, J 7.9, 0.9 Hz,
2H, HA3), 8.04 (s, 2H, HB3), 7.79 (dt, J 7.6, 2.0 Hz, 2H,
HA4), 7.26 (ddd, J 7.6, 5.1, 1.0 Hz, 2H, HA5), 5.01 (s, 2H,
OCH2), 1.67 (m, 6H, PCH2), 1.48 (m, 6H, PCH2CH2),
1.38 (sextet, J 7.6 Hz, 6H, CH2CH3), 0.87 (t, J 7.6 Hz,
9H, CH3); 13C{1H} NMR (100 MHz, CDCl3) d (ppm)
166.4 (CB4), 156.9 (CB2/A2), 156.1 (CB2/A2), 148.9 (CA6),
136.5 (CA4), 123.5 (CA5), 121.2 (CA3), 107.7 (CB3), 96.6
(C„CAu), 57.2 (OCH2), 27.1 (s, CH2CH3), 25.4 (d, JPC
33.0 Hz, PCH2), 24.1 (d, JPC 14.0 Hz, PCH2CH2), 13.5 (s,
CH3), signal for C„CAu not resolved; 31P{1H} NMR
(162 MHz, CDCl3) d (ppm) 25.7. MALDI-MS m/z 686
[M]+, 288 [MꢀAuPBu3]+. IR (m, cmꢀ1) 2955 w, 2924 w,
2862 w, 2361 w, 2130 w, 1736 w, 1558 m, 1450 m, 1404
m, 1335 m, 1188 m, 1088 m, 1018 s, 879 w, 795 m, 741
m, 617 w, 563 w, 525 w. UV/Vis kmax/nm 247, 277.
Compound 1 (0.270 g, 0.941 mmol), ClAu(dppe)AuCl
(0.405 g, 0.469 mmol) and CuI (9.4 mg, 49.4 lmol) were
added to Et3N (12 ml) and CH2Cl2 (12 ml). The reaction
mixture was stirred at room temperature for 4 d. The crude
product formed as a precipitate and was removed by filtra-
tion. It was purified by column chromatography (alumina,
CH2Cl2–acetone 90:10). One fraction was eluted and from
this, 4 was isolated as a white oil (0.253 g, 0.185 mmol,
39.4%). Crystalline 4 was obtained from a CHCl3 solution
1
left standing at room temperature. H NMR (400 MHz,
CDCl3) d (ppm) 8.63 (ddd, J 4.8, 1.8, 0.8 Hz, 4H, HA6),
8.55 (dt, J 8.0, 0.8 Hz, 4H, HA3), 8.06 (s, 4H, HB3), 7.78
(dt, J 7.6, 1.8 Hz, 4H, HA4), 7.56 (m, 8H, Ph), 7.7–7.3 (over-
lapping m, 12H, Ph), 7.25 (ddd, J 7.6, 4.8, 1.0 Hz, 4H, HA5),
5.00 (s, 4H, OCH2), 2.56 (br s, 4H, PCH2); 13C{1H} NMR
(100 MHz, CDCl3) d (ppm) 166.4 (CB4), 157.0 (CB2/A2),
156.1 (CB2/A2), 149.0 (CA6), 136.6 (CA4), 134.9 (CPhipso),
133.2 (t, JPC 7 Hz, CPh2/3), 132.1 (CPh4), 129.5 (t, JPC 5 Hz,
CPh2/3), 123.7 (CA5), 121.3 (CA3), 107.7 (CB3), 97.0
(C„CAu), 57.1 (OCH2), 23.7 (PCH2), signal for C„CAu
not resolved; 31P{1H} NMR (162 MHz, CDCl3) d (ppm)
36.5. MALDI-MS m/z 1388 [M+Na]+. IR (m, cmꢀ1) 3055
w, 2924 m, 2854 m, 1697 w, 1558 s, 1435 s, 1404 s, 1335 s,
1258 m, 1188 s, 1103 m, 1018 s, 879 s, 795 m, 725 s, 687 s.
UV/Vis kmax/nm (4.62 · 10ꢀ5 mol dmꢀ3, CH2Cl2) 233 (e/
dm3 molꢀ1 cmꢀ1 55,500), 253 sh (37,900), 277 (30,400).
2.3. Compound 3
2.5. Crystal structure determinations: general
Compound 1 (0.0820 g, 0.285 mmol), Ph3PAuCl (0.148
g, 0.299 mmol) and CuI (10.9 mg, 57.3 lmol) were added
to Et3N (12 ml) and CH2Cl2 (12 ml). The reaction mixture
was stirred at room temperature for 2 h. The precipitate that
formed was separated by filtration, and then solvent was
then removed from the filtrate to give a yellow-green oil.
Purification by column chromatography (alumina,
CH2Cl2–acetone 99:1) gave one fraction yielding 3 as a white
Data were collected on an Enraf Nonius Kappa CCD
instrument; data reduction, solution and refinement used
the programmes COLLECT [27], SIR92 [28], DENZO/SCALEPACK
[29] and CRYSTALS [30].
2.6. Crystal data for 2
C30H39AuN3OP, M = 685.60, triclinic, space group
P1, a = 11.1882(2), b = 11.3401(2), c = 14.3037(2) A,
1
ꢀ
˚
oil (0.145 g, 0.194 mmol, 68.1%). 2: H NMR (400 MHz,
CDCl3) d (ppm) 8.67 (ddd, J 4.5, 2.0, 1.2 Hz, 2H, HA6),
8.57 (dt, J 8.0, 1.2 Hz, 2H, HA3), 8.09 (s, 2H, HB3), 7.81
(dt, J 7.6, 1.6 Hz, 2H, HA4), 7.47 (m, 9H, HPh3,4), 7.41 (m,
6H, HPh2), 7.28 (ddd, J 7.2, 4.8, 1.2 Hz, 2H, HA5), 5.08 (s,
2H, OCH2); 13C{1H} NMR (125 MHz, CDCl3) d (ppm)
166.5 (CB4), 157.0 (CB2/A2), 156.2 (CB2/A2), 149.0 (CA6),
136.6 (CA4), 134.2 (d, JPC 13.8 Hz, CPh2/3), 131.5 (s, CPh4),
129.9 (d, JPC 140 Hz, C„CAu), 129.5 (d, JPC 55.0 Hz,
CPh1), 129.1 (d, JPC 11.3 Hz, CPh2/3), 123.6 (CA5),
121.3(CA3), 107.8 (CB3), 96.8 (d, JPC 26 Hz, C„CAu),
57.2 (OCH2); 31P{1H} NMR (162 MHz, CDCl3) d (ppm)
38.8. MALDI-MS m/z 748 [M]+, 289 [MꢀPh3PAu]+ (base
peak). IR (m, cmꢀ1) 3066 w, 2963 w, 2921 w, 2863 w, 2350
w, 2130 w, 1581 s, 1563 s, 1469 m, 1436 m, 1406 m, 1345
m, 1334 m, 1186 m, 1101 m, 1020 s, 795 m, 745 m, 692 s.
UV/Vis kmax/nm (2.39 · 10ꢀ5 mol dmꢀ3, CH2Cl2) 249
(e/dm3 molꢀ1 cmꢀ1 106,000), 278 (72,700).
a = 92.6970(9), b = 110.5440(7), c = 116.1495(8)ꢁ, U =
3
1480.86(5) A , Z = 2, Dcalc = 1.537 Mg mꢀ3, l(Mo-Ka) =
˚
5.047 mmꢀ1, T = 173 K, 8610 reflections collected. Refine-
ment of 8555 reflections (325 parameters) with I > 2.0rI)
converged at final R1 = 0.0315 (R1 all data = 0.0498),
wR2 = 0.0491 (wR2 all data = 0.0592), goodness-of-fit =
0.968.
2.7. Crystal data for 4 Æ 4CHCl3
C66H52Au2Cl12N6O2P2, M = 1842.49, triclinic, space
˚
ꢀ
group P1, a = 8.7136(3), b = 13.3106(4), c = 15.9758(4) A,
a = 110.037(2), b = 91.133(2), c = 95.801(2)ꢁ, U = 1728.92(9)
A , Z = 1, Dcalc = 1.770 Mg mꢀ3
,
l(Mo-Ka) = 4.797
3
˚
mmꢀ1, T = 173 K, 7916 reflections collected. Refinement
of 5094 reflections (442 parameters) with I > 3.0r I)
converged at final R1 = 0.0325 (R1 all data = 0.0626),