M.I. Bruce et al. / Journal of Organometallic Chemistry 683 (2003) 398ꢁ
/405
403
4
.2. Instrumentation
Co (m -CCÅ
/
CCÅ
3%) was isolated as brown needles. Anal. Found: C,
53.94; H, 3.69. Calc. for (C H Co O P Si): C, 53.95;
/
CSiMe )(m-dppm)(CO) (7) (57.2 mg,
3
3
3
7
7
Infrared spectra were obtained on a Bruker IFS28
FTIR spectrometer. Spectra in CH Cl were obtained
using a 0.5 mm path-length solution cell with NaCl
windows. Nujol mull spectra were obtained from
samples mounted between NaCl discs. NMR spectra
were recorded on Bruker AM300WB or ACP300 ( H at
3
Samples were dissolved in CDCl , unless otherwise
4
0
31
3
7 2
H, 3.51%; M, 890. IR (CH Cl ): n(CÅ
/
C) 2113w; n(CO)
2
2
2
2
ꢃ1
1
2061s, 2013vs, 1972 (sh) 1954 (sh) cm . H-NMR: d
0.36 (s, 9H, SiMe ), 3.46 (m, 1H, CH ), 4.35 (m, 1H,
3
2
1
3
CH ), 7.26ꢁ
/
7.43 (m, 20H, Ph). C-NMR: d 0.26 (s,
SiMe ), 43.26 [t, J(CP) 35.4, CH ÃP], 90.62 (s, C ),
/
2
1
/
3
2
o
1
00.13, C at 75.47, P at 121.503 MHz) instruments.
3
31
57.11 (s, C ), 98.58 (s, C ), 103.45 (s, C ), 128.66ꢁ
d
g
b
135.19 (m, Ph), 201.76, 209.99, 215.57 [3ꢄ
/s (br), CO].
3
3
1
stated, contained in 5 mm sample tubes. Chemical shifts
are given in ppm relative to internal tetramethylsilane
P-NMR: d 34.92 (s, dppm). ESMS (negative ion, with
ꢃ
MeOH, m/z): 890, [M] ; (with NaOMe, m/z): 817,
ꢃ
1
for H- and C-NMR spectra and external H PO for
13
[Mꢃ
/SiMe ] .
3
3
4
3
1
P-NMR spectra. ES mass spectra: VG Platform 2 or
Finnigan LCQ. Solutions were directly infused into the
instrument. Chemical aids to ionisation were used as
required [14]. Elemental analyses were performed by
CMAS, Melbourne, Australia.
4.3.3. {[(tol) P]Au}CÅ
/
CCÅ
/
CC{Co (m-dppm)(CO) }
3 7
3
(6)
A solution of NaOMe (twofold excess) in MeOH (1
ml) was added to Co (m -CCÅ
/
CCÅCSiMe )(m-
/
3
3
3
dppm)(CO) (100 mg, 0.11 mmol) in THF/MeOH (1/3,
4 ml). After 1 h at r.t., spot t.l.c. showed that all starting
complex had been consumed. AuCl{P(tol) } (59 mg,
7
4
.3. Reagents
3
The
compounds
CCÅ
CSiMe ){P(tol) } [10], FcCÅ
Co (m -CBr)(m-dppm)(CO)
0.11 mmol) was then added and the reaction mixture
was stirred for 1 h to give a brown precipitate under a
brown supernatant. The precipitate was filtered off,
washed with MeOH and dried in air. Crystallisation
3
3
7
[
11],{Cp(OC) W}CÅ
/
/
C{Au(PPh )} [10], Au(CÅ
/
3
3
CCÅ
/
/
CI [14] were prepared
3
3
using the cited methods.
(
CH Cl ꢁMeOH) gave very dark red crystals of
/
2
2
4
(
.3.1. {Cp(OC) W}CÅ
/
CCÅ
/
CC{Co (m-dppm)(CO) }
3
{[(tol) P]Au}CÅ
/
CCÅ
mg), an extra 2.3 mg (total yield 68.5%) being obtained
from the mother liquor by preparative t.l.c. (acetoneꢁ
/
CC{Co (m-dppm)(CO) } (6) (99.1
3
7
3
3
7
5)
A mixture of {Cp(OC) W}CÅ
/
CCÅ
/
C{Au(PPh )} (50
3
/
3
mg, 0.06 mmol), Co (m -CBr)(m-dppm)(CO) (57 mg,
hexane 3:7). Anal. Found: C, 52.86; H, 3.30. Calc. for
(C H AuCo O P ): C, 52.83; H, 3.27%; M, 1318. IR
3
3
7
0
.06 mmol), Pd(PPh ) (7 mg, 0.006 mmol) and CuI (1
3
4
58 43
3
7 3
mg, 0.005 mmol) in THF (7 ml) was stirred at room
temperature (r.t.) for 3 h, after which time the solution
had turned brown. Purification by preparative t.l.c.
(CH Cl ): n(CÅ
/
C) 2115w; n(CO) 2059s, 2010vs, 1986
2
2
ꢃ1
1
(sh), 1967 (sh) cm . H-NMR: d 2.46 (s, 9H, Me),
3.44, 4.46 (2ꢄm, 2ꢄ1H, CH ), 7.16ꢁ7.56 (m, 32H,
C H ). C-NMR: d 21.43 (s, Me), 40.79 [t, J(CP)
/
/
/
2
1
3
(
acetoneꢁ
/
hexane 3:7) gave a major brown band (Rf
CC{Co (m-
Phꢂ
/
6
4
0
dppm)(CO) } (5) (66.4 mg, 91%) was isolated as dark
;42) from which {Cp(OC) W}CÅ
/
CCÅ
/
20, CH P], 67.92 [s(br), C ], 89.09 [s(br), C ], 92.55
2 o d
3
3
[s(br), C ], 100.31 [s(br), C ], 201.95, 210.21, 221.79
g b
7
3
s (br), CO]. P-NMR: d 33.36 [s(br), dppm], 40.19
1
red crystals (CHCl ). Anal. Found: C, 45.30; H, 1.97.
3
[3ꢄ
/
Calc. for (C H Co O P W×
/
0.5CHCl ): C, 45.12; H,
3
[s(br), P(tol) ]. ESMS (negative ion, with NaOMeꢁ
/
4
5
27
3
10
2
3
ꢃ
2
2
3
7
.27%; M, 1150. IR (CH Cl ): n(CÅ
/
C) 2117w; n(CO)
MeOH, m/z): 1317, [MꢃH] .
/
2
2
058s, 2037m, 2008vs, 1955m (br) cmꢃ1. H-NMR: d
1
.36 (m, 1H, CH ), 4.43 (m, 1H, CH ), 5.71 (s, 5H, Cp),
2
4.3.4. Co (m -CCÅ
/
CCÅ
A mixture of {(Ph P)Au}CÅCC{Co (m-dppm)(CO) }
/
/
CFc)(m-dppm)(CO) (8)
2
3
3
7
1
7.47 (m, 20H, Ph). C-NMR: d 39.13 (s, br,
3
.09ꢁ
/
/
3
3
7
dppm), 91.91 (s, Cp), 210.19 (s, CO); other peaks at
5
(75 mg, 0.06 mmol), FcCÅ
CI (20 mg, 0.06 mmol),
3
3.48, 96.01, 114.03 (carbons of C chain). P-NMR: d
1
Pd(PPh ) (3.5 mg, 0.003 mmol) and CuI (1 mg, 0.006
mmol) in THF (10 ml) was stirred at r.t. for 1 h.
Evaporation and purification of the residue by prepara-
5
3 4
3
4.56 (s, dppm). ESMS (positive ion, with NaOMe, m/
ꢂ
ꢂ
z): 1173, [Mꢂ
Naꢃ
/
Na] ; 1145, [Mꢂ
/
Naꢃ
/
CO] ; 1117, [Mꢂ
/
ꢂ
ꢃ
/
2CO] ; (negative ion, MeOH, m/z): 1150, [M]
tive t.l.c. (acetoneꢁ/hexane 1:4) gave two bands. The
faster moving (R 0.93) contained FcCÅ
/
CCÅCFc (1.2
/
f
4
.3.2. Co (m -CCÅ
/
CCÅ
/
CSiMe )(m-dppm)(CO) (7)
3
mg, 5%), identified by comparison with an authentic
sample. The major product was contained in the
3
3
7
A solution containing Au(CÅ
/
CCÅ
/
CSiMe ){P(tol) }
3
3
(50 mg, 0.09 mmol), Co (m -CBr)(m-dppm)(CO) (76
mg, 0.09 mmol), Pd(PPh ) (3 mg, 0.003 mmol) and CUI
brownꢁ
CCÅCCÅ
dark red crystals (C H ꢁhexane). Anal. Found: C,
6
/
orange band (Rf 0.26), which gave Co (m -
3
3
7
3
3
/
/
CFc)(m-dppm)(CO) (8) (51.7 mg, 87%) as
/
3
4
7
(
1 mg, 0.005 mmol in THF (7 ml) was stirred at r.t.for 1
6
h. Work-up by preparative t.l.c. (CH Cl ꢁhexane 1:2)
/
59.22; H, 3.15. Calc. for (C H Co FeO P ×C H ): C,
2 /
2
2
47 31
3
7
6
6
gave a major brownꢁ
/
green band (R 0.59) from which
58.88; H, 3.43%; M, 1002. IR (CH Cl ): n(CÅ
/
C) 2157w,
f
2
2
Bruce, Michael I.
