5
740 Organometallics, Vol. 15, No. 26, 1996
Whittall et al.
7
8
1
1
1
1
.40-7.63 (m, 19H, Ph, H
.26 (d, J HH ) 9 Hz, 2H, H11). C NMR (δ, 75 MHz, CDCl
24.1 (C11), 125.8 (C ), 127.0, 127.5 (C , C10), 129.2 (d, J CP
1 Hz, C ), 129.6 (d, J CP ) 56 Hz, C , partly obscured by C
), 133.0 (C ), 134.3 (d, J CP ) 14 Hz, C ), 136.7 (C
), 147.1 (C12). P NMR (δ, 121 MHz, CDCl
4
, H
5
), 7.71 (d, J HH ) 9 Hz, 2H, H10),
Ta ble 1. Cr ysta llogr a p h ic Da ta for Com p lexes
3 a n d 4
1
3
3
):
3
5
)
3
4
m
i
m
),
),
empirical formula
Mr
C26H19AuNO2P
605.38
C32H23AuNO2P
681.48
31.6 (C
46.9 (C
p
4
o
6
3
1
9
3
): 43.0.
cryst color, habit
yellow, block
0.2 × 0.2 × 0.1
P21/c (No. 14)
8.650(3)
18.555(5)
14.179(2)
pale yellow, prism
0.4 × 0.2 × 0.1
P 1h (No. 2)
8.818(3)
9.810(3)
15.649(4)
84.18(2)
89.55(2)
89.43(3)
1346.7(6)
2
FAB MS [m/ z (fragment, relative intensity)]: 1140 ([M + Au-
3
cryst dimens (mm )
space group
a (Å)
b (Å)
c (Å)
+
+
+
2
(PPh
3
)] , 9), 782 ([M + H] , 18), 721 ([Au(PPh
3
)
] , 18), 459
+
([M - CtCC
6
H
4
C
6
H
4
NO
2
] , 100). Crystals of 4 suitable for
diffraction analysis were grown by slow diffusion of ethanol
into a dichloromethane solution at room temperature.
Au ((E)-4,4′-CtCC
,4′-HCtCC CHdCHC
dissolved in a 1:1 mixture of acetone and dichloromethane
5 mL). AuCl(PPh ) (59 mg, 0.12 mmol) and a methanol
6
H
4
CHdCHC
6
H
4
NO
2
)(P P h
3
) (5). (E)-
R (deg)
â (deg)
91.15(2)
4
6
H
4
6
H
4
NO (30 mg, 0.12 mmol) was
2
γ (deg)
3
V (Å )
2275.3(8)
4
1.767
(
3
Z
-
1
solution of sodium methoxide (5 mL, 0.5 mol L ) were added,
and the mixture was stirred at room temperature for 16 h.
Removal of the dichloromethane and acetone under reduced
Dcalc (g cm-3)
-1
1.681
µ (cm
)
65.81 (Mo KR)
55.31 (Mo KR)
0.67-1.00
none
4781
3774
transm factors
0.71-1.00
pressure precipitated
which was collected by filtration (73 mg, 85%). Anal. Calc
for C34 25AuNO P: C, 57.71; H, 3.57; N, 1.98. Found: C,
7.16; H, 3.34; N, 2.11. IR (CH
a
yellow microcrystalline product,
-9
secondary extinction
9(5) × 10
N
4179
2800
281
H
2
No (I > 3.00σ(I))
no. variables
-1
5
2
-
Cl
2
): ν(CtC) 2112 cm . UV-
334
1
-1
-1
p-factor
0.001
0.024
0.017
0.001
0.029
0.032
vis: λ (thf) 386 nm, ꢀ 38 000 M cm , 303 nm, ꢀ 20 000 M
cm ; (CH
7
7
-
1
1
R
3
CN) 376, 301 nm. H NMR (δ, 300 MHz, CDCl
.08 (d, J HH ) 16 Hz, 1H, H15), 7.21 (d, J HH ) 16 Hz, 1H, H16),
.41-7.61 (m, 21H, Ph, H , H , H10), 8.19 (d, J HH ) 9 Hz, 2H,
11). C NMR (δ, 75 MHz, CDCl
, C10), 129.1 (d, J CP ) 11 Hz, C
3
):
Rw
4
5
1
3
i p 9 4 5 10
Hz, C ), 131.6 (C ), 131.9 (C ), 131.5, 132.2, 132.4 (C , C , C ),
H
3
): 124.1 (C11), 125.4 (C
3
),
),
3
1
1
1
1
26.0 (C15), 126.7, 126.8 (C
5
m
134.3 (d, J CP ) 14 Hz, C
o
), 146.8 (C12). P NMR (δ, 121 MHz,
29.5 (d, J CP ) 56 Hz, C
34.3 (d, J CP ) 14 Hz, C
i
), 131.6 (C
), 134.5 (C
p
), 132.8 (C
), 143.9 (C
4
), 133.0 (C16),
), 146.6 (C12).
CDCl ): 43.0. FAB MS [m/ z (fragment, relative intensity)]:
3
+
+
1164 ([M + Au(PPh
3
)] , 8), 721 ([Au(PPh
3
)
2
] , 27), 706 ([M +
, 100).
) (8). AuCl(PPh
NdCHC NO (30
o
6
9
3
1
H]
+
, 16), 459 ([M - CtCC H CtCC H NO ]
+
P NMR (δ, 121 MHz, CDCl
relative intensity)]: 721 ([Au(PPh
59 ([M - CtCC CHdCHC
Au ((Z)-4,4′-CtCC CHdCHC
) (100 mg, 0.20 mmol) and (Z)-4,4′-HCtCC
NO (60 mg, 0.24 mmol) were dissolved in dichlo-
3
): 43.0. FAB MS [m/ z (fragment,
6
4
6
4
2
+
+
3
)
2
] , 70), 708 ([M + H] , 29),
Au (4,4′-CtCC
6
H
4
NdCHC
6
H
4
NO
2
)(P P h
H
3
3
)
+
4
6
H
4
6
H
4
NO
2
] , 100).
(50 mg, 0.10 mmol) and 4,4′-HCtCC
6
4
6
H
4
2
H
4
6
H
4
NO
2
)(P P h
3
) (6). AuCl-
CHd
mg, 0.12 mmol) were dissolved in dichloromethane (5 mL). A
methanol solution of sodium methoxide (5 mL, 0.50 M) was
added, and the mixture was stirred at room temperature for
16 h. Removal of the dichloromethane under reduced pressure
precipitated a yellow microcrystalline powder, which was
recrystallized from dichloromethane/ethanol to afford yellow
6
(
PPh
3
6
6 4
H
CHC
H
4
2
romethane (5 mL). A methanol solution of sodium methoxide
-
1
(6 mL, 0.50 mol L ) was added, and the mixture was stirred
at room temperature for 16 h. The solvent volume was
reduced to 2 mL to afford a yellow microcrystalline solid, which
was collected and recrystallized from dichloromethane/ethanol
crystals (60 mg, 85%). Anal. Calc for C33
2 2
H24AuN O P: C,
55.94; H, 3.42; N, 3.95. Found: C, 56.06; H, 3.24; N, 3.82. IR
-1
(113 mg, 80%). Anal. Calc for C34
H
25AuNO
2
P: C, 57.71; H,
2 2
(CH Cl ): ν(CtC) 2115 cm . UV-vis: λ (thf) 392 nm, ꢀ 21 000
-
1
-1
-1
-1
3
Cl
.57; N, 1.98. Found: C, 57.40; H, 3.36; N, 1.79. IR (CH
2
-
M
cm , 297 nm, ꢀ 32 000 M cm ; (CH
H NMR (δ, 300 MHz, CDCl ): 7.17 (d, J HH ) 8 Hz, 2H, H
7.40-7.60 (m, 17H, Ph, H ), 8.04 (d, J HH ) 9 Hz, 2H, H10),
8.30 (d, J HH ) 9 Hz, 2H, H11), 8.54 (s, 1H, H16). C NMR (δ,
75 MHz, CDCl ): 120.9 (C ), 123.9 (C ), 124.0 (C11), 129.1 (d,
CP ) 11 Hz, C ), 129.3 (C10), 129.6 (d, J CP ) 56 Hz, C ), 131.6
(C ), 133.3 (C ), 134.3 (d, J CP ) 14 Hz, C ), 141.6 (C ), 149.0,
149.1 (C , C12). P NMR (δ, 121 MHz, CDCl ): 43.0. FAB
3
CN) 377, 290 nm.
-
1
1
): ν(CtC) 2114 cm . UV-vis: λ (cyclohexane) 369, 301
3
4
),
2
-
1
-1
-1
nm; (thf) 362 nm, ꢀ 20 000 M cm , 298 nm, ꢀ 28 000 M
cm ; (CH
6
7
7
J
5
-
1
1
13
3
CN) 360, 292 nm. H NMR (δ, 300 MHz, CDCl
.54 (d, J HH ) 12 Hz, 1H, H15), 6.74 (d, J HH ) 12 Hz, 1H, H16),
.08 (d, J HH ) 9 Hz, 2H, H ), 7.36 (d, J HH ) 9 Hz, 2H, H10),
.37 (d, J HH ) 9 Hz, 2H, H ), 7.41-7.56 (m, 15H, Ph), 8.04 (d,
HH ) 9 Hz, 2H, H11). C NMR (δ, 75 MHz, CDCl ): 123.5
11), 124.5 (C ), 127.8 (C15), 128.5, 129.6 (C , C10), 129.1 (d,
CP ) 11 Hz, C ), 129.6 (d, J CP ) 56 Hz, C ), 131.6 (C
), 133.6 (C16), 134.2 (d, J CP ) 14 Hz, C ), 134.4 (C
), 146.4 (C12). P NMR (δ, 121 MHz, CDCl
3
):
3
5
3
J
m
i
4
5
p
4
o
9
1
3
31
3
6
3
(C
3
5
MS [m/ z (fragment, relative intensity)]: 1167 ([M + Au-
+
+
+
J
m
i
p
6
), 132.4
), 144.1
): 43.0. FAB
(PPh
3
)] , 13), 721 ([Au(PPh
NdCHC
3
)
2
] , 31), 709 ([M + H] , 22), 459
2
+
(C
4
9
o
([M - CtCC
6
H
4
6
H
4
NO
] , 100).
3
1
(C
3
X-r a y Str u ctu r e Deter m in a tion s. Unique diffractometer
data sets were obtained using the ω-2θ scan technique
(graphite-monochromated Mo KR radiation; 0.710 69 Å; 2θmax
) 50.1°; 295 K) and yielded N independent reflections, No
of these with I g 3.00σ(I) being considered “observed” and
used in full matrix least-squares refinement; an empirical
ψ-type absorption correction was applied in each case. Aniso-
tropic thermal parameters were refined for the non-hydrogen
MS [m/ z (fragment, relative intensity)]: 1166 ([M + Au-
+
+
+
(
(
PPh
[M - CtCC
Au (4,4′-CtCC
50 mg, 0.10 mmol) and 4,4′-HCtCC
.12 mmol) were dissolved in dichloromethane (10 mL).
3
)] , 11), 721 ([Au(PPh
CHdCHC
CtCC
3
)
H
2
] , 19), 708 ([M + H] , 31), 459
+
6
H
4
6
4
NO
2
] , 100).
6
H
4
6
H
4
NO
2
)(P P h
3
) (7). AuCl(PPh
3
)
(
0
6
H
4
CtCC
6
H
4
NO (30 mg,
2
A
-
1
methanol solution of sodium methoxide (3 mL, 0.50 mol L
)
was added, and the mixture was stirred at room temperature
for 16 h. Removal of the dichloromethane under reduced
pressure precipitated a yellow microcrystalline powder (58 mg,
atoms; (x, y, z, Uiso
values. Conventional residuals R and R
)
H
were included constrained at estimated
on |F| are given;
), where σ (F ) ) [S (C
) ]/Lp (S ) scan rate, C ) peak count, B )
w
2
2
2
2
2
2
the weighting function w ) 4F
o
/σ (F
o
o
2
2
2
8
1
2
2%). Anal. Calc for C34
H
23AuNO
2
P: C, 57.88; H. 3.29; N,
Cl ): ν(CtC)
115 cm . UV-vis: λ (cyclohexane) 361, 303 nm; (thf) 362
+ 4B) + (pF
o
.99. Found: C, 57.60; H, 3.15; N, 1.95. IR (CH
2
2
background count, p ) p factor determined experimentally
from standard reflections), was employed. Computation
used the teXsan package. Specific data collection, solution,
and refinement parameters are given in Table 1. Pertinent
-
1
-
1
-1
-1
-1
21
nm, ꢀ 36 000 M cm , 301 nm, ꢀ 32 000 M cm ; (CH
3
CN)
): 7.41-7.57 (m,
), 7.62 (d, J HH ) 9 Hz, 2H, H10), 8.19 (d, J HH
Hz, 2H, H11). 13C NMR (δ, 75 MHz, CDCl
): 120.1 (C ), 123.5
11), 126.0 (C ), 129.2 (d, J CP ) 11 Hz, C ), 129.5 (d, J CP ) 56
1
3
1
9
55, 298 nm. H NMR (δ, 300 MHz, CDCl
9H, Ph, H , H
3
4
5
)
3
6
(21) Single Crystal Structure Analysis Software, Version 1.6c; Mo-
lecular Structure Corp.: The Woodlands, TX, 1993.
(C
3
m