3956 Inorganic Chemistry, Vol. 49, No. 8, 2010
Lane et al.
added to a solution of Au(THT)(Cl) (562 mg, 1.75 mmol) in
20 mL of methylene chloride. The resulting solution was stirred
for 30 min; then the solvent was removed under vacuum, yield-
ing a white solid, which was recrystallized from CH2Cl2/ether at
-21 °C to give a pure white solid (663 mg, 94%).
J=31, Ar), 34.5 (CH, i-Pr), 33.3 (br, CH, i-Pr), 24.8 (CH3, i-Pr),
24.5-24.2 (m, CH2), 24.2 (overlapping previous peak, CH3,
i-Pr), 23.6 (CH3, i-Pr). IR: 2960, 2925, 2868, 2416 (PH), 1676,
1600, 1560, 1460, 1423, 1385, 1364, 1318, 1262, 1194.
(PhHP(CH2)3PHPh)(AuCl)2 (9). Under N2, to a solution of
Au(THT)(Cl) (494 mg, 1.54 mmol) in 12 mL of CH2Cl2 was
added a solution of PhHP(CH2)3PHPh (4; 201 mg, 0.773 mmol)
in 12 mL of CH2Cl2. The resulting mixture was stirred for 15 min
and then filtered through Celite to remove a brown impurity.
The solvent was removed under vacuum to give a white solid,
which was recrystallized three times from methylene chloride/
ether to remove THT, finally yielding a white solid (545 mg,
97%).
Anal. Calcd. for C21H30Au2Cl2P2: C, 31.17; H, 3.74. Found:
C, 30.89; H, 3.62. MS m/z calcd. for C21H30Au2Cl2P2: 808.05;
m/z calcd. for C21H30Au2ClP2 (M - Cl)þ = 773.08. FAB-MS
(NBA) m/z = 773.1. 31P{1H} NMR (CD2Cl2): δ -38.3, -38.5,
1
1.1:1 ratio of diastereomers. H NMR (CD2Cl2): δ 7.02 (8H,
Ar), 6.28 (overlapping br dt, JPH =394, 7, 4H, PH), 2.59 (24H,
CH3), 2.35 (12H, CH3), 2.28-2.17 (m, 8H, CH2), 1.92-1.82 (m,
4H, CH2). 13C{1H} NMR (CD2Cl2): δ 142.7 (Ar), 141.6 (d, J=
9, Ar), 130.8 (d, J=9, Ar), 119.0 (d, J=15, Ar, a), 118.5 (d, J=
15, Ar, b), 110.0 (Ar), 25.1 (d, J=11, CH2), 24.5-24.2 (m, CH2),
23.4 (d, J = 11, CH3), 21.2 (CH3). IR: 2932, 2845, 2409 (PH),
1600, 1556, 1441, 1376, 1289, 1246, 1186, 1066, 1022, 946, 853,
695, 673, 619, 548, 537.
Anal. Calcd for C15H18Au2Cl2P2 0.1Et2O: C, 25.25; H, 2.61.
3
Found: C, 25.43; H, 2.52. The presence of ether was confirmed
quantitatively by integration of the H NMR spectrum (CD2-
1
Cl2). MS m/z calcd. for C15H18Au2Cl2P2: 723.96; m/z calcd. for
C15H18Au2ClP2 (M - Cl)þ =688.99. Found: FAB-MS (NBA)
m/z=688.9. 31P{1H} NMR (CD2Cl2): δ -8.9, -9.2; 1.1:1 ratio
of diastereomers. 1H NMR (CD2Cl2): δ 7.72-7.64 (m, 4H, Ar),
(IsHP(CH2)3PHIs)(AuCl)2 (7). Under N2, a solution of IsPH-
(CH2)3PHIs (2; 104 mg, 0.203 mmol) in 12 mL of CH2Cl2 was
added to a solution of Au(THT)(Cl) (133 mg, 0.415 mmol) in
12 mL of CH2Cl2. The resulting solution was stirred for 30 min;
then the solvent was removed under vacuum, yielding a white solid
(225 mg, 91%). Recrystallization from methylene chloride gave
7.58-7.54 (m, 2H, Ar), 7.49-7.45 (m, 4H, Ar), 6.19 (br dt, JPH
=
400, 6, 1H, PH, a), 6.16 (br dt, JPH = 400, 6, 1H, PH, b),
2.44-2.37 (br m, 4H, CH2), 1.93-1.89 (br m, 2H, CH2). 13C-
{1H} NMR (CD2Cl2): δ 134.4 (d, J=5, Ar, a), 134.3 (d, J=5,
Ar, b), 132.7 (Ar), 129.9-129.8 (m, Ar), 124.6 (br d, J=63, Ar),
26.0-25.6 (m, CH2), 23.0 (d, J=33, CH2). IR: 3041, 2910, 2355
(PH), 1812, 1572, 1480, 1436, 1398, 1305, 1246, 1186, 1110, 989,
864, 739, 690.
1
a solvate, as observed by H NMR (CDCl3). Quantifying the
amount of CH2Cl2 by NMR spectroscopy was not possible be-
cause the samples appeared to lose CH2Cl2 on standing. Elemental
analyses of different samples were consistent with the presence of
one or fewer equiv of CH2Cl2: Anal. Calcd. for C33H54Au2-
(1,10-C5H4PHPh)2Fe)(AuCl)2 (10). Under nitrogen, to a so-
lution of Au(THT)Cl (203 mg, 0.633 mmol) in 12 mL of CH2Cl2
was added a solution of 1,10-(PHPh)2C5H4FeC5H4 (5; 129 mg,
0.321 mmol) in 12 mL of CH2Cl2. The resulting dark orange
solution was stirred for 35 min. The solvent was removed under
vacuum to yield a dark orange solid, which was recrystallized
from CH2Cl2/ether at -60 °C to yield a yellow solid (222 mg,
81%).
Anal. Calcd. for C22H20Au2Cl2P2Fe: C, 30.48; H, 2.33.
Found: C, 30.21; H, 2.26. 31P{1H} NMR (CDCl3): δ -10.3,
-11.0; 1.2:1 ratio of diastereomers. 1H NMR (CDCl3): δ
7.74-7.66 (m, 7H, Ar), 7.57-7.48 (br m, 13H, Ar), 7.12 (d,
JPH=406, 4H, PH, overlapping Ar signals), 4.83 (4H, Cp), 4.80
(2H, Cp), 4.78 (2H, Cp), 4.75-4.74 (br m, 4H, Cp), 4.66 (2H,
Cp), 4.54 (2H, Cp). 13C{1H} NMR (CDCl3): δ 133.8 (d, J=14,
Ar), 133.5 (d, J=14, Ar), 132.5 (d, J=16, Ar), 129.7 (d, J=3,
Ar), 129.6 (d, J=3, Ar), 77.7 (d, J=20, Cp), 76.6 (d, J=11, Cp),
76.1 (d, J=18, Cp), 75.6 (m, Cp), 75.0-74.4 (m, Cp). IR: 3052,
2932, 2845, 2355 (PH), 1654, 1474, 1431, 1387, 1305, 1262, 1175,
1104, 1028, 902, 886, 831, 739, 695, 635.
Cl2P2 0.5CH2Cl2: C, 39.45; H, 5.43. Found: C, 39.15; H, 5.64.
3
Anal. Calcd. for C33H54Au2Cl2P2 0.75CH2Cl2: C, 38.93; H, 5.37.
3
Found: C, 38.96; H, 5.38. Anal. Calcd. for C33H54Au2-
Cl2P2 1CH2Cl2: C, 38.43; H, 5.31. Found: C, 38.20; H, 5.32.
3
HRMS m/z calcd. for C33H54Au2ClP2 (M - Cl)þ: 941.2721.
Found: 941.2707. 31P{1H} NMR (CDCl3): δ -42.8, -43.0, 1:1
ratio of diastereomers. 1H NMR (CD2Cl2): δ 7.16 (d, J = 4, 4H,
Ar), 7.14 (d, J=4, 4H, Ar), 6.42 (br dm, JPH=390, 4H, PH), 3.52
(br, 4H, CH2), 2.96-2.90 (m, 4H, CH), 2.32-2.20 (br m, 8H, CH),
2.05-1.99 (m, 4H, CH2), 1.36 (d, J=6, 12H, CH3), 1.34 (d, J=6,
12H, CH3), 1.29 (overlapping d, J = 7, 12H, CH3), 1.28
(overlapping d, J = 7, 12H, CH3), 1.272 (overlapping d, J = 7,
12H, CH3), 1.269 (overlapping d, J = 7, 12H, CH3). 13C{1H}
NMR (CD2Cl2): δ 153.7 (Ar), 152.5 (Ar), 123.2 (d, J = 9, Ar),
117.1 (d, J=31, Ar), 116.6 (d, J=31, Ar), 34.6 (CH, i-Pr), 33.4 (br,
CH, i-Pr), 26.7-26.3 (m, CH2), 25.3 (d, J = 13, CH2), 24.59
(overlapping, CH3, i-Pr), 24.58 (overlapping, CH3, i-Pr), 24.23
(CH3, i-Pr), 24.21 (CH3, i-Pr), 23.66 (overlapping, CH3, i-Pr),
23.63 (overlapping, CH3, i-Pr). IR: 2960, 2924, 1652, 1601, 1558,
1540, 1495, 1456, 1419, 1385, 1363. A PH stretching vibration
could not be confidently assigned.
[Au(MesP)(CH2)3(PMes)Au]4 (11). A solution of MesHP-
(AuCl)(CH2)3PHMes(AuCl) (6, 115 mg, 0.142 mmol) in 10 mL
of CH2Cl2 was treated with 15 mL of aqueous NH4OH (0.3 M,
3.8 mmol, 27 equiv) and then stirred for 30 min, which led to the
formation of an orange oil in a clear solution. A pipet was used to
collect the oil, which was refrigerated overnight at -21 °C to yield a
white precipitate. The remaining orange oil was removed using a
pipet. The white precipitate was treated with 5 mL of CH2Cl2 to
extract any residual orange oil, and the mixture was cooled in the
refrigerator for another hour. The CH2Cl2 was then removed using
a pipet, and the precipitate was dried under vacuum to yield a white
solid. The combined orange oils were recooled as above, and this
process was repeated once more to yield the product (70 mg, 67%).
In a larger-scale procedure with a slightly modified workup,
to a solution of 6 (324 mg, 0.4 mmol) in 15 mL of CH2Cl2 was
added slowly, with gentle stirring, 15 mL of aqueous NH4OH
(0.5 M, 10 mmol, 25 equiv). The mixture was stirred slowly for
4.5 h during which time a white precipitate developed at the
interface of the aqueous and CH2Cl2 layers. The CH2Cl2 layer
became yellow-orange and was extracted and concentrated
under reduced pressure then cooled over 8 days at -28 °C to
(IsHP(CH2)2PHIs)(AuCl)2 (8). Under N2, a solution of
IsPH(CH2)2PHIs (3; 189 mg, 0.379 mmol) in 12 mL of CH2Cl2
was added to a solution of Au(THT)(Cl) (244 mg, 0.761 mmol)
in 12 mL of CH2Cl2. The resulting solution was stirred for 30 min,
during which it changed from clear to a light yellow color, and
finally to pink. The mixture was filtered through Celite, yielding
a light yellow solution. The solvent was removed under vacuum
to give a white solid containing visible black impurities. Recrys-
tallization from CH2Cl2/ether at -21 °C gave an off-white solid
(239 mg, 65%).
Anal. Calcd. for C32H52Au2Cl2P2: C, 39.89; H, 5.44. Found:
C, 39.53; H, 5.27. HRMS m/z calcd. for C32H52Au2ClP2
(M-Cl)þ: 927.2564. Found: 927.2527. 31P{1H} NMR
1
(CD2Cl2): δ -39.1. H NMR (CD2Cl2): δ 7.13 (4H, Ar), 6.54
(br dm, JPH=392, 2H, PH), 3.48 (br, 4H, CH), 2.91 (sept, J=7,
2H, CH), 2.43 (m, 2H, CH2), 2.25-2.21 (m, 2H, CH2), 1.35 (d,
J=7, 12H, CH3), 1.26-1.24 (overlapping d, J=7, 12H, CH3),
1.12 (d, J = 6, 12H, CH3). 13C{1H} NMR (C6D6): δ 153.4
(br, Ar), 153.3 (Ar), 123.0 (Ar), 117.0 (3-line pattern, apparent