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Can. J. Chem. Vol. 79, 2001
failed to find any evidence for the generation of an interme-
diate containing an alkynyl(hydrido)rhodium moiety
RhH(CϵCR)Cl(P-i-Pr3)2 as a building block, and therefore a
concerted mechanism is most likely (6). This result is
in contrast to that for the isomerization reaction of
trans-[RhCl(HCϵCtBu)(P-i-Pr3)2] to trans-[RhCl(=CϵCH-t-Bu)
(P-i-Pr3)2] for which a five-coordinate intermediate [RhH(C
ϵC-t-Bu)Cl(P-i-Pr3)2] could not only be detected but even
isolated (7).
tained. Yield: 298 mg (85%). IR (kBr) (cm–1): ν(C=C) 1600.
1H NMR (400 MHz, CD2Cl2) δ: 7.21 (s, C6H4), 5.08, 5.06
(both t, J (PH) = 3.6 Hz, =CH), 4.19, 4.11, 4.04, 3.77 (all m,
CH2OCH3), 3.84, 3.82, 3.64 (all s, OCH3), 2.86, 2.48, 2.37,
2.32, 2.20, 2.01, 1.89 (all m, PCHCH3 and PCH2), 1.54–1.28
(br m, PCHCH3). 13C NMR (100.6 MHz, CD2Cl2) δ: 355.5
(dd, J (PC) = 18.1 and 15.1 Hz, Ru=C), 127.1, 126.3 (both s,
C6H4), 121.4 (q, J (FC) = 320.9 Hz, CF3), 117.8 (s, =CH),
72.7, 71.7 (both s, CH2OCH3), 63.2, 63.1, 61.8 (all s,
OCH3), 37.5 (d, J (PC) = 33.3 Hz, PCHCH3), 28.6, 28.5
(both d, J (PC) = 26.0 Hz, PCHCH3), 26.6 (d, J (PC) =
31.2 Hz, PCHCH3), 25.8 (d, J (PC) = 20.0 Hz, PCHCH3),
25.7 (d, J (PC) = 19.0 Hz, PCH2), 23.3 (d, J (PC) = 23.6 Hz,
PCH2), 20.1, 19.8, 19.75, 19.7, 19.6, 19.2, 19.1, 19.0 (all s,
PCHCH3). 31P NMR (162.0 MHz, CD2Cl2) δ: 68.1, 56.2
(both d, J (PP) = 24.3 Hz). 19F NMR (376.5 MHz, CD2Cl2)
δ: –78.6 (s). Anal. calcd. for C48H90Cl2F6O10P4Ru2S2: C
41.11, H 6.47, S 4.57; found: C 41.37, H 6.30, S 4.42.
Experimental
All experiments were carried out under an atmosphere of
argon by using standard Schlenk techniques. The starting
materials [RuCl2{κ2(P,O)-i-Pr2PCH2CH2OMe}2] (1) (1),
C6H4(CϵCH)2-p and -m (4, 5) (8), [RuCl-(C=CHC6H4CϵCH-
m){κ2(P,O)-i-Pr2PCH2CH2OMe}2](CF3SO3) (2) (1), and
[RhCl(P-i-Pr3)2]2 (8) (9) were prepared as described previ-
ously. IR spectra were recorded on a PerkinElmer 1420 IR
spectrometer and NMR spectra on Bruker AC 200 and WM
400 instruments. Melting points (dec. temp.) were deter-
mined by DTA.
Preparation of [RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2(C=CHC6H4-m-CH=C)RuCl{κ2(P,O)-
i-Pr2PCH2CH2OMe}2](CF3SO3)2 (7)
The procedure was analogous to that described for 3, us-
ing 1 (262 mg, 0.50 mmol), 5 (31 mg, 0.25 mmol), and
CF3SO3Ag (128 mg, 0.50 mmol) in 20 mL of acetone as
starting materials. An orange microcrystalline solid was ob-
tained. Yield: 161 mg (46%). IR (KBr) (cm–1): ν(C=C) 1610,
1580. 1H NMR (400 MHz, CD2Cl2) δ: 7.22–6.95 (br m,
C6H4), 5.06, 5.05 (both t, J (PH) = 3.7 Hz, =CH), 4.20, 4.12,
4.04, 3.80 (all m, CH2OCH3), 3.87, 3.82, 3.65 (all s, OCH3),
2.88, 2.48, 2.42, 2.33, 2.22, 2.03, 1.91 (all m, PCHCH3 and
PCH2), 1.55–1.28 (br m, PCHCH3). 13C NMR (100.6 MHz,
CD2Cl2) δ: 357.4 (dd, J (PC) = 19.1 and 15.1 Hz, Ru=C),
129.5, 129.4, 129.3, 127.2, 125.7, 125.5, 123.0, 122.8 (all s,
C6H4), 121.4 (q, J (FC) = 319.9 Hz, CF3), 117.8, 117.7
(both s, =CH), 72.8, 72.7, 71.7 (all s, CH2OCH3), 63.2, 63.1,
61.7 (all s, OCH3), 37.5 (d, J (PC) = 31.2 Hz, PCHCH3),
29.6, 29.4 (both d, J (PC) = 26.3 Hz, PCHCH3), 26.7, 26.5
(both d, J (PC) = 28.8 Hz, PCHCH3), 25.7 (d, J (PC) =
20.2 Hz, PCHCH3), 25.6 (d, J (PC) = 19.6 Hz, PCH2), 23.3
(d, J (PC) = 23.0 Hz, PCH2), 20.2, 20.1, 19.7, 19.65, 19.6,
19.1, 19.0, 18.9 (all s, PCHCH3). 31P NMR (162.0 MHz,
CD2Cl2) δ: 68.0, 56.1 (both d, J (PP) = 24.3 Hz). 19F NMR
(376.5 MHz, CD2Cl2) δ: –78.6 (s). Anal. calcd. for
C48H90Cl2F6O10P4Ru2S2: C 41.11, H 6.47, S 4.57; found: C
41.49, H 6.21, S 4.49.
Preparation of [RuCl(C=CHC6H4-p-CϵCH){κ2(P,O)-i-
Pr2PCH2CH2OMe}2](CF3SO3) (3)
A solution of 1 (262 mg, 0.50 mmol) and 4 (63 mg,
0.50 mmol) in 10 mL of acetone was cooled to 0°C and then
treated with CF3SO3Ag (128 mg, 0.50 mmol). After the re-
action mixture was stirred for 20 min in the dark, the precip-
itate (AgCl) was separated by filtration through Kieselgur
and the filtrate concentrated to ca. 0.5 mL in vacuo. A yel-
low microcrystalline solid was formed which was washed
twice with ether and dried. Yield: 275 mg (72%). IR (KBr)
(cm–1): ν(ϵCH) 3200, ν(CϵC) 2080, ν(C=C) 1620, 1590. H
1
NMR (400 MHz, CD2Cl2) δ: 7.37, 7.30 (AB spin system, J
(HH) = 7.8 Hz, C6H4), 5.09 (t, J (PH) = 3.2 Hz, =CH), 4.18,
4.13, 4.04, 3.80 (all m, CH2OCH3), 3.84, 3.65, (both s,
OCH3), 3.10 (s, ϵCH), 2.88, 2.50, 2.40, 2.34, 2.30, 2.00,
1.85 (all m, PCHCH3 and PCH2), 1.53–1.29 (br m,
PCHCH3). 13C NMR (100.6 MHz, CD2Cl2) δ: 355.5 (dd,
J (PC) = 18.1 and 15.1 Hz, Ru=C), 132.7, 130.5, 126.5,
119.9 (all s, C6H4), 121.4 (q, J (FC) = 320.9 Hz, CF3), 117.2
(s, =CHR), 83.8 (s, CϵCH), 77.4 (s, CϵCH), 72.8, 71.7
(both s, CH2OCH3), 63.2, 63.1, 61.7, 61.6 (all s, OCH3),
37.7 (d, J (PC) = 33.2 Hz, PCHCH3), 29.5 (d, J (PC) =
26.0 Hz, PCHCH3), 26.6 (d, J (PC) = 28.6 Hz, PCHCH3),
25.8 (d, J (PC) = 20.0 Hz, PCHCH3), 25.4 (d, J (PC) =
22.0 Hz, PCH2), 23.2 (d, J (PC) = 24.0 Hz, PCH2), 20.1,
Preparation of [RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2(C=CHC6H4-m-CϵCH)RhCl(P-i-
Pr3)2](CF3SO3) (9)
19.8, 19.7, 19.65, 19.6, 19.5, 19.1, 19.0 (all s, PCHCH3). 31
P
NMR (162.0 MHz, CD2Cl2) δ: 67.9, 56.3 (both d, J (PP) =
24.1 Hz). 19F NMR (376.5 MHz, CD2Cl2) δ: –78.6 (s). Anal.
calcd. for C29H48ClF3O5P2RuS: C 45.58, H 6.33, S 4.19;
found: C 45.19, H 6.22, S 4.22.
A solution of 8 (101 mg, 0.11 mmol) in 15 mL of freshly
distilled THF was cooled to –60°C and then treated with 2
(160 mg, 0.21 mmol). A characteristic change of color from
violet to orange-yellow occurred. After the reaction mixture
was warmed to room temperature and stirred for 10 min, the
solvent was removed, the remaining orange solid washed
three times with 5 mL portions of pentane (–20°C), and
dried in vacuo. Yield: 159 mg (62%), mp 114°C (dec.). IR
(CH2Cl2) (cm–1): ν(ϵCH) 3070, ν(CϵC) 1790, ν(C=C) 1570.
1H NMR (200 MHz, CD2Cl2) δ: 7.59–6.75 (br m, C6H4),
5.10 (t, J (PH) = 3.1 Hz, =CH), 4.16, 4.14, 4.02, 3.83 (all m,
Preparation of [RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2(C=CHC6H4-p-CH=C)RuCl{κ2(P,O)-
i-Pr2PCH2CH2OMe}2](CF3SO3)2 (6)
The procedure was analogous to that described for 3, us-
ing 1 (262 mg, 0.50 mmol), 4 (31 mg, 0.25 mmol), and
CF3SO3Ag (128 mg, 0.50 mmol) in 20 mL of acetone as
starting materials. An orange microcrystalline solid was ob-
© 2001 NRC Canada