H. G. Raubenheimer et al.
2 CO]+, 264 (45) [M Cl]+.
2 CO
FULL PAPER
NCH3), 2.67 (s, 3 H, CCH3) ppm. 13C NMR (CDCl3): δ = 238.0 Cl]+, 302 (5) [M
–
–
–
(br. s, Ccarbene), 225.7 (s, COtrans), 219.9 (s, COcis), 155.1 (s, CPh),
147.0 (s, CCH), 143.3 (s, CCH3), 134.7 (s, i-Ph), 130.9 (s, NCH),
129.9 (s, o-Ph), 128.2 (s, m-Ph), 127.9 (s, p-Ph), 42.7 (s, NCH3),
C13H17ClNO2Rh·0.5H2O (366.65): calcd. C 42.6, H 5.0, N 3.8;
found C 42.3, H 5.2, N 3.6.
18.8 (s, CCH ) ppm. IR (ATR): ν
= 2036 [s, A1(1)], 1958 (sh,
Synthesis of 5: The complex [AuCl(PPh3)] was prepared in situ from
[AuCl(Me2S)] (58 mg, 0.20 mmol) and PPh3 (52 mg, 0.20 mmol) in
10 mL of acetonitrile and the suspension was stirred at room tem-
perature for 45 min. Separately, a solution of 2 in 20 mL of acetoni-
trile was prepared. Both Schlenk tubes were cooled to –45 °C. Solid
NaOTf (34 mg, 0.20 mmol) was added to the solution of
[AuCl(PPh3)]. After 10 min the solution of 2 was transferred to the
Schlenk tube containing the [AuCl(PPh3)] via a Teflon cannula.
Stirring continued for 4 h whereupon the cooling bath reached
room temperature and the colour of the solution lightened to le-
mon yellow. TLC analysis (silica gel adsorbent, diethyl ether as
eluent) showed that almost all chromium carbene had reacted and
an apolar yellow side product, assumed to be [Cr(CO)5(Me2S)], had
formed. All volatiles were removed in vacuo and the resultant solid
was re-dissolved in CH2Cl2. A filterstick filtration and stripping of
the solvent afforded a yellow residue which was extracted with tolu-
ene to remove most of the side product. Crystallisation from a
CH2Cl2 solution layered with pentane gave colourless needles suit-
able for X-ray diffraction. Yield 78%, 0.12 g, m.p. 225 °C, slight
onset of decomposition noticeable from 205 °C (dec.). 1H NMR
˜
3
ν(CO)
B1), 1871 [vs, E and A1(2)] cm–1. IR (CH Cl ): ν
= 2041 [s,
˜
ν(CO)
2
2
A1(1)], 1957 (sh, B1), 1916 [vs, E and A1(2)] cm–1. MS (FAB): m/z
(%) = 375 (10) [M]+, 347 (16) [M – CO]+, 263 (23) [M – 4 CO]+,
235 (19) [M – 5 CO]+. C18H13CrNO5 (375.30): calcd. C 57.6, H 3.5,
N 3.7; found C 57.7, H 3.7, N 3.5.
Synthesis of 3: Compound 3 was prepared in the same fashion as 1
from [W{=C(OMe)CH=C(NHMe)Me}(CO)5] (2.01 g, 4.50 mmol)
and ethynylbenzene (1.2 g, 1.3 mL, 11.8 mmol). The Rf values of 3
and its precursor are virtually identical. Yield 20% (based on last
alkyne addition step), 0.48 g, m.p. 178 °C (dec.). 1H NMR
(1CD2Cl2/4CDCl3): δ = 8.66 (s, 1 H, CCH), 7.45 (m, 5 H, Ph), 7.36
(s, 1 H, NCH), 3.86 (s, 3 H, NCH3), 2.56 (s, 3 H, CCH3) ppm. 13C
1
NMR (1CD2Cl2/4CDCl3): δ = 218.9 (s, Ccarbene), 206.3 (s, d, JW,C
1
= 127.3 Hz, COtrans), 201.5 (s, d, JW,C = 127.3 Hz, COcis), 155.6
(s, CPh), 149.6 (s, CCH), 145.0 (s, CCH3), 138.6 (s, i-Ph), 133.3 (s,
NCH), 130.7 (s, o-Ph), 129.1 (s, m-Ph), 128.9 (s, p-Ph), 43.9 (s,
NCH ), 19.7 (s, CCH ) ppm. IR (ATR): ν
= 2049 [s, A1(1)],
˜
ν(CO)
3
3
1962 (s, B1), 1856 [vs, E and A1(2)] cm–1. IR (CH Cl ): ν
=
˜
ν(CO)
2
2
2052 [m, A1(1)], 1914 [vs, E and A1(2)] cm–1. MS (FAB): m/z (%) =
507 (5) [M]+, 479 (7) [M – CO]+, 423 (14) [M – 3 CO]+.
C18H13NO5W (507.14): calcd. C 42.6, H 2.6, N 2.8; found C 43.0,
H 3.0, N 2.5.
1
(CD2Cl2): δ = 8.40 (s, d, JC,H = 183.8 Hz, 1 H, CCH), 8.06 (s, d,
1
1 H, JC,H = 167.9 Hz, NCH), 7.81 (m, 2 H, o-Ph), 7.55 (m, 6 H,
1
o-PPh3), 7.44 (m, 12 H, m,p-Ph, m,p-PPh3), 4.20 (s, d, JCH
=
1
144.3 Hz, 3 H, NCH3), 2.73 (s, d, JC,H = 130.5 Hz, 3 H, CCH3)
ppm. 13C NMR (CD2Cl2): δ = 199.5 (br. s, Ccarbene), 149.4 (s, CPh),
147.7 (s, CCH), 141.1 (s, i-Ph), 140.4 (s, CCH3), 140.2 (s, NCH),
134.4 (d, 2JP,C = 14.0 Hz, o-PPh3), 132.3 (d, 4JP,C = 1.9 Hz, p-PPh3)
Synthesis of 4: A Schlenk tube was charged with 1 (0.081 g,
0.228 mmol), [Rh2(µ-Cl)2(CO)4] (0.022 g, 0.057 mmol) and CH2Cl2
(20 mL) and connected to a bubbler. The solution was stirred for
5 h at room temperature until no CO formation was observed any-
more as indicated by the bubbler. The mixture had turned from
yellow to black. The mixture was filtered through Celite and the
resulting filtrate was layered with diethyl ether and stored at –20 °C
overnight. The precipitate was separated by filtration and the re-
sulting filtrate dried in vacuo to afford a mixture of cis-4 and trans-
4 (0.050 g). No separation of the isomers was possible. Crystallisa-
tion of the mixture by dissolving a small amount in CH2Cl2 and
layering it with pentane afforded a few orange-yellow single crystals
of cis-4.
1
3
130.3 (d, JP,C = 62.4 Hz, i-PPh3), 129.7 (d, JP,C = 11.5 Hz, m-
PPh3), 129.7 (s, o-Ph), 129.3 (s, m-Ph), 129.0 (s, p-Ph), 121.5 (q,
–
1JC,F = 321 Hz, CF3SO3 ), 45.7 (s, NCH3), 20.1 (s, CCH3) ppm.
31P NMR (CD2Cl2): δ = 41.8 (s) ppm. MS (FAB): m/z (%) = 642
(100) [M – CF3SO3]+, 459 (17) [M – CF3SO3 – PPh3]+, 380 (47)
[AuPPh3]+. C32H28AuF3NO3PS (791.58): calcd. C 48.6, H 3.6, N
1.8; found C 49.0, H 3.5, N 1.6.
Synthesis of 6: Two Schlenk tubes were charged with [AuCl(tht)]
(93 mg, 0.29 mmol) and 3 (150 mg, 0.29 mmol), respectively. Both
compounds were dissolved in 10 mL of CH2Cl2 each and the solu-
tions were cooled to –35 °C. The [AuCl(tht)] solution was transfer-
red to the carbene complex solution via a Teflon cannula. After
the cooling bath had reached 0 °C (2 h), it was removed and the
solution stirred at room temperature for another 1.5 h. Completion
of the reaction was indicated by TLC (silica adsorbent, CH2Cl2/
diethyl ether, 1:1 as mobile phase) when starting material was not
detected any more and instead a spot at Rf 0.83 that can be attrib-
uted to [W(CO)5(tht)] [Rf(3) = 0] was observed. All volatiles were
removed in vacuo, the residue redissolved in 30 mL of CH2Cl2,
filtered and concentrated to about 7 mL. Layering the solution
with pentane yielded 85 mg (71%) of a cream-coloured microcrys-
talline solid. A crystal suitable for X-ray diffraction was obtained
1
trans-4: Yield (according to NMR): 44%. H NMR (CD2Cl2): δ =
8.11 (s, 1 H, CCH), 7.60 (s, 1 H, NCH), 3.94 (s, 3 H, NCH3), 3.04
(m, 2 H, CH2CH2CH2CH3), 2.54 (s, 3 H, CCH3), 1.80 (m, 2 H,
CH2CH2CH2CH3), 1.48 (m, 2 H, CH2CH2CH2CH3), 1.02 (m, 3 H,
2
CH2CH2CH2CH3) ppm. 13C NMR (CD2Cl2): δ = 211.0 (d, JRh,C
2
= 31.9 Hz, Ccarbene), 188.3 (d, JRh,C = 50.9 Hz, CO), 150.3 [s,
C(nBu)], 141.8 (s, CCH), 138.8 (s, CCH3), 135.3 (s, NCH), 44.1 (s,
NCH3), 37.8 (s, CCH3), 33.1 (s, CH2CH2CH2CH3), 23.0 (s,
CH2CH2CH2CH3), 19.5 (s, CH2CH2CH2CH3), 14.1 (s,
CH CH CH CH ) ppm. IR (CH Cl ): ν
= 1905 (s) cm–1.
˜
ν(CO)
2
2
2
3
2
2
cis-4: Yield (according to NMR): 56%. 1H NMR (CD2Cl2): δ =
7.89 (s, 1 H, CCH), 7.51 (s, 1 H, NCH), 3.90 (s, 3 H, NCH3), 3.04 by recrystallising a small quantity from thf layered with pentane.
(m, 2 H, CH2CH2CH2CH3), 2.50 (s, 3 H, CCH3), 1.71 (m, 2 H, Yield 71%, 0.085 g, m.p. 154 °C (dec.). 1H NMR (CD2Cl2): δ =
CH2CH2CH2CH3), 1.48 (m, 2 H, CH2CH2CH2CH3), 1.02 (m, 3 H, 7.99 (s, 1 H, CCH), 7.96 (s, 1 H, NCH), 7.82 (m, 2 H, o-Ph), 7.48
2
CH2CH2CH2CH3) ppm. 13C NMR (CD2Cl2): δ = 209.2 (d, JRh,C (m, 3 H, m,p-Ph), 3.98 (s, 3 H, NCH3), 2.55 (s, 3 H, CCH3) ppm.
13C NMR (CD2Cl2): δ = 186.5 (s, Ccarbene), 149.0 (s, CPh), 146.1
(s, CCH), 141.8 (s, CCH3), 141.2 (s, NCH), 138.7 (s, i-Ph), 129.5
(s, o-Ph), 129.0 (s, m-Ph), 128.9 (s, p-Ph), 45.0 (s, NCH3), 19.9 (s,
CCH3) ppm. MS (FAB): m/z (%) = 380 (100) [M – Cl]+.
2
= 9.9 Hz, Ccarbene), 192.2 (d, JRh,C = 4.9 Hz, COtrans), 186.1 (d,
2JRh,C = 9.7 Hz, COcis), 149.7 [s, C(nBu)], 141.8 (s, CCH), 139.6 (s,
CCH3), 135.3 (s, NCH), 44.4 (s, NCH3), 38.5 (s, CCH3), 33.1 (s,
CH2CH2CH2CH3), 22.8 (s, CH2CH2CH2CH3), 19.5 (s,
CH2CH2CH2CH3), 14.1 (s, CH2CH2CH2CH3) ppm. IR (CH2Cl2): C13H13AuClN (415.67): calcd. C 37.6, H 3.2, N 3.4; found C 37.5,
ν
˜
ν(CO) = 2046 (s), 1983 (s) cm–1. MS (FAB): m/z (%) = 322 (7) [M –
H 3.3, N 3.1.
1910
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