L. Weber et al. / Journal of Organometallic Chemistry 643–644 (2002) 81–88
87
dicarboxylate were purchased commercially. NMR
spectra were recorded in C6D6 on a Bruker Avance
DRX 500 (1H, 13C, 29Si, 31P) spectrometer using SiMe4
or 85% H3PO4 as external standard. IR spectra were
recorded on Bruker FTIR IFS66 and FTIR Vector 22
instruments.
0.52 ml of a 2 M solution of HC(N2)SiMe3 and 0.65 ml
of a 1.6 M solution of methyllithium) in 10 ml of Et2O
was added dropwise to the chilled solution (−50 °C) of
3b (0.65 g, 1.04 mmol) in Et2O (25 ml). The reaction
mixture was warmed up to room temperature and then
freed from volatile components in vacuo. The residue
was triturated with n-pentane (15 ml) and filtered. The
filtrate was stored at −4 °C to afford 4b as red–brown
air- and moisture-sensitive crystals (0.54 g, 74% yield).
Anal. Found: C, 56.64, H, 6.01; N, 4.00. Calc. for
C33H43AsFeN2O3Si2: C, 56.41; H, 6.17; N, 3.99%. IR
(KBr): w(NN) 2025 s; w(CO) 1980 s, 1937 s; l(SiMe3)
4.2. [Cp*(CO)2FeP(Cl){C(OSiMe3)ꢀCPh2] (3a)
A solution of diphenylketene (0.68 g, 3.5 mmol) in 10
ml of n-pentane was added dropwise to a chilled solu
tion (−50 °C) of [Cp*(CO)2FeP(SiMe3)2] (1.48 g, 3.5
mmol) in 25 ml of n-pentane. Warming up to ambient
temperature was followed by the addition of solid
hexachloroethane (0.83 g, 3.5 mmol) and the resulting
mixture was stirred for 18 h. It was concentrated to ca.
10 ml, filtered, and the filtercake was dried in vacuo to
give 3a as an air- and moisture-sensitive orange solid
(1.73 g, 85% yield). Anal. Found: C, 59.68; H, 5.92.
Calc. for C29H34ClFeO3PSi: C, 59.96; H, 5.90%. IR
1
1245 m; z(SiMe3) 846 m cm−1. H-NMR: l=0.21 (s,
9H, OSiCH3
C5CH3), 6.93 (t, JHH=7.5 Hz, 2H, PhꢁH
(m, 4H, PhꢁH), 7.46–7.49 (m, 4H, PhꢁH
NMR: l= −0.1 (s, CSiCH3), 1.0 (s, OSiC
C5CH3), 20.8 (s, CN2), 95.3 (s, C5CH3), 126.3 (s, PhꢁC
126.6 (s, PhꢁC), 128.7 (s, CPh2), 131.2 (s, PhꢁC), 132.2
(s, PhꢁC), 142.2 (s, PhꢁC
AsꢁCꢀC), 217.3 (s, FeCO), 217.4 (s, FeC
l=1.0 (CSiMe3), 17.9 (OSiMe3).
6 ), 0.39 (s, 9H, CSiCH6 3), 1.42 (s, 15H,
3
6
6
), 7.07–7.18
6
6
). 13C{1H}-
6
6
H3), 9.1 (s,
),
6
6
6
6
6
6
6
6
6
1), 144.0 (s, PhꢁC
6
1), 163.2 (s,
(KBr) w(CO) 2003 s, 1951 s; l(SiMe3) 1256 s; z(SiMe3)
6
6
6
O). 29Si-NMR:
1
861 m cm−1. H-NMR: l=0.27 (s, 9H, SiCH3
6
), 1.33
), 7.04–7.13
), 7.45 (d, 3JHH=6.9 Hz, 2H, PhꢁH
),
7.53 (d, 3JHH=7.6 Hz, 2H, PhꢁH). 13C{1H}-NMR:
H3), 8.9 (d, JPC=7.0 Hz, C5CH3), 97.1
5CH3), 126.7 (s, PhꢁC), 126.8 (s, PhꢁC), 128.1 (s,
PhꢁC Ph2), 131.1 (s,
), 129.3 (d, 2JPC=39.1 Hz, C
PhꢁC), 131.35 (s, PhꢁC), 131.40 (s, PhꢁC), 141.9 (d,
3JPC=4.6 Hz, PhꢁC1), 143.0 (d, 3JPC=11.5 Hz,
PhꢁC ꢀC), 216.2 (s,
1), 163.4 (d, 1JPC=75.9 Hz, PꢁC
FeC
O), 216.4 (d, 3JPC=5.7 Hz, FeCO). 29Si-NMR:
l=19.8 (s, OSi). 31P{1H}-NMR: l=264.5 (s, FeP
Cl).
(s, 15H, C5CH3
6 ), 6.93–6.96 (m, 1H, PhꢁH6
¸¹¹¹¹¹¹¹¹¹¹¹¹¹¹º
(m, 5H, PhꢁH
6
6
4.5. [Cp*(CO)2FeSb{NNꢀC(SiMe3)C(CO2Me)ꢀC-
(CO2Me)}{C(OSiMe3)ꢀCPh2] (9c)
6
3
l=1.2 (s, SiC
6
6
(s, C
6
6
6
A sample of dimethyl acetylenedicarboxylate (0.13 g,
0.95 mmol) was added to the chilled solution (0 °C) of
4c (0.71 g, 0.95 mmol) in 30 ml of n-pentane. The
mixture was stirred at 0 °C, then warmed up to ambient
temperature and concentrated to ca. 10 ml. It was
filtered, and the filtercake was dried in vacuo to afford
product 9c as an orange moisture- and air-sensitive
solid (0.75 g, 88% yield). Anal. Found: C, 52.32; H,
5.67; N, 3.13. Calc. for C39H49FeN2O7SbSi2: C, 52.54;
H, 5.54; N, 3.14%. IR (KBr): w(CO) 1996 s, 1942 s;
6
6
6
6
6
6
6
6
6
6
6
4.3. [Cp*(CO)2FeAs(Cl){C(OSiMe3)ꢀCPh2] (3b)
Analogously product 3b was obtained as an air- and
moisture-sensitive solid (2.38 g, 79%) from the reaction
of 2.26 g (4.8 mmol) of [Cp*(CO)2FeAs(SiMe3)2] with
diphenylketene (0.94 g, 4.8 mmol) and treatment of the
resulting mixture with hexachloroethane (1.14 g, 4.8
mmol). Anal. Found: C, 55.40; H, 5.47. Calc. for
C29H34AsClFeO3Si: C, 55.74; H, 5.48%. IR (KBr)
w(COester) 1709 s; l(SiMe3) 1246 m; z(SiMe3) 847 m
1
cm−1. H-NMR: l= −0.14 (s, 9H, CSiCH3
6
), 0.65 (s,
), 3.48 (s, 3H,
), 6.92–7.21 (m, 6H,
), 7.53 (d, 3JHH=7.5 Hz, 2H, PhꢁH
), 7.78 (d,
3JHH=7.5 Hz 2H, PhꢁH). 13C{1H}-NMR: l= −0.7
(s, CSiCH3), 0.2 (s, OSiCH3), 9.1 (s, C5CH3), 50.7 (s,
CO2CH3), 52.1 (s, CO2CH3), 95.1 (s, C5
ArꢁC), 126.5 (s, ArꢁC), 127.3 (s, C
ArꢁC), 132.4 (s, ArꢁC
ArꢁC), 141.9 (s, ArꢁC
ArꢁC), 163.9 (s, SbꢁCꢀC), 164.3 (s, C
O2CH3), 214.0 (s, FeCO), 214.9 (s, FeC
l= −7.6 (CSiMe3), 19.5 (OSiMe3).
9H, OSiCH
CO2CH3), 3.77 (s, 3H, CO2CH3
PhꢁH
6 3), 1.32 (s, 15H, C5CH6 3
6
6
6
6
6
6
6
6
w(CO) 2000 s, 1948 s; l(SiMe3) 1255 m; z(SiMe3) 859
6
6
6
CH3), 121.2 (s,
6 Ph2), 130.7 (s,
1
m cm−1. H-NMR: l=0.29 (s, 9H, SiCH3
6
), 1.34 (s,
). 13C{1H}-
H3), 96.3 (s,
6
6
6
6
15H, C5CH3
NMR: l=1.3 (s, SiC
C5CH3), 126.8 (s, PhꢁC
Ph2), 130.9 (s, PhꢁC), 131.6 (s, PhꢁC
PhꢁC1), 142.0 (s, PhꢁC1), 164.6 (s, AsꢁC
FeCO), 216.5 (s, FeC
O). 29Si-NMR: l=20.5 (OSi).
6
), 6.95–7.54 (m, 10H, PhꢁH
H3), 9.0 (s, C5C
), 127.2 (s, PhꢁC
6
6
6
), 133.8 (s, ArꢁC
), 146.0 (s, ArꢁC
6
), 141.5 (s,
6
6
6 ), 156.7 (s,
O2CH3), 164.4 (s,
O). 29Si-NMR:
6
6
6
), 129.3 (s,
), 141.5 (s,
6
6
6
C
6
6
6
C6
6
6
6
6
6 ꢀC), 215.6 (s,
6
6
¸¹¹¹¹¹¹¹¹¹¹¹¹¹¹º
4.6. [Cp*(CO)2FeSb{NNꢀC(SiMe3)C(CO2Et)ꢀC-
(CO2Et)}{C(OSiMe3)ꢀCPh2] (9d)
4.4. [Cp*(CO)2FeAs{C(N2)SiMe3}{C(OSiMe3)ꢀCPh2]
(4b)
Analogously, 0.99 g (83% yield) of orange solid 9d
were synthesized from 0.97 g (1.3 mmol) of 4c and 0.22
A freshly prepared solution of LiC(N2)SiMe3 (from
Weber, Lothar
