1
1
FT/IR-410 spectrometer. H, H–1H COSY, 31P{1H}, 13C{1H}
[Ru(ꢁ2-C2H3SCH2Ph)(cod)(depe)] 2c. Depe (0.087 cm3, 0.38
NMR, DEPT and H–13C correlation spectra were obtained
on a JEOL LA300 spectrometer. H NMR chemical shifts are
mmol); benzyl vinyl sulfide (60.4 mg, 0.403 mmol); 1 (121.3 mg,
0.3851 mmol); complex 2c was obtained as an orange-brown
oil and could not be crystallised (145.0 mg, 0.231 mmol): yield
60%. Selected NMR data: 31P{1H} NMR (121.6 MHz, C6D6)
shows two AB quartets in a 2.6:1 ratio: δ 63.7 (d, J = 22 Hz),
63.3 (d, J = 22 Hz); δ 58.9 (d, J = 23 Hz), 57.1 (d, J = 23 Hz).
1
1
reported in ppm downfield of tetramethylsilane as internal
standard. 31P{1H} NMR chemical shifts are relative to an
external standard, 85% H3PO4 in D2O. Solid state 31P{1H}
NMR studies were performed on a Chemagnetics CMX400
spectrometer (operating at 161.03 MHz) using a cylindrical
rotor and spun at 3 kHz; chemical shifts are reported relative to
NH4H2PO4. Elemental analysis was performed with a Perkin-
Elmer 2400 Series II CHNS analyser. Gases were quantitatively
analysed by gas chromatography (Shimadzu GC-8A, GC-14B)
using the internal standard method.
1
Extensive overlapping of signals in the H NMR spectrum
of 2c prevented detailed assigment of the vinyl, cod and depe
resonances for both isomers.
[Ru(ꢁ2-C2H3SEt)(cod)(depe)] 2d. depe (0.08 cm3, 0.35 mmol);
ethyl vinyl sulfide (0.0365 cm3, 0.36 mmol); 1 (114.9 mg, 0.3648
mmol); 2d was crystallised from ethanol, methanol or hexane
to afford a yellow solid (128.1 mg, 0.269 mmol): yield 74.3%.
Selected NMR data: 1H NMR (300 MHz, C6D6) shows
two isomers in 2.5:1 ratio = Major isomer vinyl resonances:
Preparation of [Ru(ꢁ2-C2H3YR)(cod)(depe)] (Y ؍
O, S)
[Ru(ꢁ2-C2H3OPh)(cod)(depe)] 2a. A typical example is given:
depe (0.125 cm3, 0.553 mmol) and phenyl vinyl ether (0.067
cm3, 0.55 mmol) was added to a solution of [Ru(cod)(cot)]
1 (171.2 mg, 0.5435 mmol) in 3 cm3 of toluene. The reaction
mixture was stirred at room temperature for 24 h. After volatile
materials were removed, the residual dark yellow oil was
crystallised from warm hexane to give white crystals which were
dried under vacuum to yield 2 (255.0 mg, 0.4779 mmol): yield
88%. Anal. Calc. for C26H44OP2Ru: C, 58.30; H, 8.28. Found:
C, 58.21; H, 8.29%. Selected NMR data: 31P{1H} NMR (121.6
MHz, C6D6) shows three AB quartets in a 23:3:1 ratio: δ 63.3
(d, J = 26 Hz), 62.8 (d, J = 26 Hz); δ 61.0 (d, J = 24 Hz), 59.5 (d,
J = 24 Hz); δ 58.2 (d, J = 26 Hz), 52.2 (d, J = 26 Hz). Extensive
overlapping of signals in the 1H NMR spectrum of 2a
prevented detailed assignment of the vinyl, cod and depe
resonances for both isomers.
δ 2.82 (br dq, 1H, J = 6.3, 3.0 Hz, SCH᎐CHH ), 1.90 (m, 1H,
᎐
cis
SCH᎐CHH ), 1.70 (m, 1H, SCH᎐CH ). Minor isomer vinyl
᎐
᎐
trans
2
resonances: δ 2.45 (br dq, 1H, J = 7.5, 4.2 Hz, SCH᎐CHH ),
᎐
cis
2.20 (ddt, J = 10.2, 7.2, 2.7 Hz, SCH᎐CHHtrans), 1.30 (m, 1H,
᎐
SCH᎐CH ). Other resonances: 2.74 (q, J = 7.2 Hz, SCH CH of
᎐
2
2
3
major isomer), 2.70 (q, J = 7.5 Hz, SCH2CH3 of minor isomer).
Extensive overlapping of signals prevented detailed assignment
of the cod and depe resonances for both isomers. 31P{1H}
NMR (121.6 MHz, C6D6) shows two AB quartets in a 2.5:1
ratio: Major isomer: δ 63.8 (d, J = 23 Hz), 63.0 (d, J = 23 Hz).
Minor isomer: δ 59.1 (d, J = 23 Hz), 57.3 (d, J = 23 Hz).
[Ru(ꢁ2-C2H3SCHMe2)(cod)(depe)] 2e. Depe (0.06 cm3, 0.27
mmol); isopropyl vinyl sulfide (25.2 mg, 0.247 mmol); 1 (83.7
mg, 0.266 mmol); 2e was crystallised from acetone to afford a
yellow solid (126.7 mg, 0.2445 mmol): yield 92.0%. Anal. Calc.
for C23H46SP2Ru: C, 53.36; H, 8.96; S, 6.19. Found: C, 53.26;
The following complexes were prepared similarly. The
amount of reactants used, yields, analytical and NMR data
are summarised below:
1
H, 9.10; S, 5.75%. Selected NMR data: H NMR (300 MHz,
C6D6) shows two isomers in a 2.6:1 ratio: Major isomer vinyl
[Ru(ꢁ2-C2H3SPh)(cod)(depe)] 2b. Depe (0.130 cm3, 0.575
mmol); phenyl vinyl sulfide (0.08 cm3, 0.61 mmol); 1 (184.7 mg,
0.5863 mmol); 2b (233.4 mg, 0.5863 mmol): yield 72.5%. Anal.
Calc. for C26H44SP2Ru: C, 56.60; H, 8.04; S, 5.81. Found:
C, 56.97; H, 8.45; S, 5.95%. 1H NMR (300 MHz, C6D6) shows
two isomers in a 1.8:1 ratio: Major isomer vinyl resonances:
resonances: δ 2.83 (dq, 1H, J = 6.3, 3.2 Hz, SCH᎐CHH ),
᎐
cis
2.05 (m, 1H, SCH᎐CHH ), 1.70 (m, 1H, SCH᎐CH ). Minor
᎐
᎐
trans
2
isomer vinyl resonances: δ 2.58 (br dq, 1H, J = 8.3, 4.2 Hz,
SCH᎐CHH ), 2.48 (ddt, J = 10.2, 7.2, 2.7 Hz, SCH᎐CHHtrans),
᎐
᎐
cis
2.15 (m, 1H, SCH᎐CH ). 31P{1H} NMR (121.6 MHz, C6D6)
᎐
2
shows two AB quartets in a 2.6:1 ratio: Major isomer: δ 63.6
(d, J = 23 Hz), 62.8 (d, J = 23 Hz). Minor isomer: δ 59.1
(d, J = 23 Hz), 57.1 (d, J = 23 Hz). 13C{1H} NMR (75.5 MHz,
C6D6) shows resonances of two isomers: Major: δ 99.6 (dd,
J = 17, 3 Hz, CH of cod), 76.6 (dd, J = 8, 4 Hz, CH of cod),
54.3 (dd, J = 8, 3 Hz, CH of cod), 53.5 (d, J = 6 Hz, CH of cod),
δ 3.03 (dq, 1H, J = 6.5, 3.3 Hz, SCH᎐CHH ), 1.97 (m, 1H,
᎐
cis
SCH᎐CHH ), 1.75 (m, 1H, SCH᎐CH ). Minor isomer vinyl
᎐
᎐
trans
2
resonances: δ 2.66 (ddt, 1H, J = 10.5, 7.1, 3.0 Hz, SCH᎐CH-
᎐
Htrans), 2.53 (br dq, J = 8.1, 4.2 Hz, SCH᎐CHH ), 2.14 (m, 1H,
᎐
cis
SCH᎐CH ). Other resonances: δ 7.77 (m, 2H, o-SPh of both
᎐
2
isomers), 7.19–7.12 (m, 2H, m-SPh of both isomers), 6.94–6.88
(m, 1H, p-SPh of both isomers), 4.30 (m, CH of cod of minor
isomer), 3.74 (m, CH of cod of major isomer), 3.56 (m, CH
of cod of minor isomer), 3.39–3.04 (m, CH of cod of both
isomers), 2.38–0.40 (m, CH ϩ CH2 of cod and depe of both
isomers). 31P{1H} NMR (121.6 MHz, C6D6) shows two AB
quartets: Major isomer: δ 63.3 (d, J = 22 Hz), 62.6 (d, J = 22
Hz). Minor isomer: δ 58.4 (d, J = 22 Hz), 55.9 (d, J = 22 Hz).
13C{1H} NMR (75.5 MHz, C6D6) shows resonances of two
isomers: Major: δ 147.2 (s, ipso-SPh), 128.5 (s, m-SPh), 125.8
(s, o-SPh), 123.6 (s, p-SPh), 100.1 (dd, J = 16, 3 Hz, CH of cod),
77.2 (d, J = 5 Hz, CH of cod), 55.1 (dd, J = 7, 3 Hz, CH of
cod), 54.2 (d, J = 7 Hz, CH of cod), 41.7 (d, J = 6 Hz, CH2 of
41.7 (d, J = 4 Hz, CH of cod), 36.5 (d, J = 2 Hz, SCH᎐CH ),
᎐
2
2
36.3 (s, CH2 of cod), 36.2 (dd, JCP = 11, 5 Hz, SCH᎐CH ), 29.5
᎐
2
(t, J = 3 Hz, CH2 of cod), 26.3 (s, CH2 of cod), 23.7 (s,
SCHMe2). Minor: δ 96.7 (brd, J = 15 Hz, CH of cod), 77.3 (dd,
J = 8, 5 Hz, CH of cod), 54.0 (dd, J = 7, 3 Hz, CH of cod), 53.1
(d, J = 5 Hz, CH of cod), 41.4 (d, J = 6 Hz, CH2 of cod), 35.5
(s, SCH᎐CH ), 35.4 (s, CH of cod), 33.1 (dd, JCP = 11, 5 Hz,
᎐
2
2
SCH᎐CH ), 30.1 (s, CH of cod), 27.1 (s, CH of cod), 23.4
᎐
2
2
2
(s, SCHMe2).
Reaction of [Ru(ꢁ2-C2H3SPh)(cod)(depe)] 2b with PhSC2D3
A 5 mm NMR tube was charged first with a solid sample of
2b (11.8 mg, 0.0198 mmol) under a nitrogen atmosphere and
C6D6 (0.5 cm3). Then, PhSC2D3 (5 mg, 0.0360 mmol) was added
cod), 36.1 (d, JCP = 6 Hz, SCH᎐CH ), 36.3 (s, CH of cod),
᎐
2
2
34.3 (dd, JCP = 7, 3 Hz, SCH᎐CH ), 29.3 (s, CH of cod), 26.2
᎐
2
2
1
by hypodermic syringe. H and 31P{1H} NMR spectra showed
(s, CH2 of cod). Minor: δ 147.5 (s, ipso-SPh), 128.5 (s, m-SPh),
125.7 (s, o-SPh), 123.3 (s, p-SPh), 97.0 (dd, J = 16, 3 Hz, CH of
cod), 77.1 (d, J = 5 Hz, CH of cod), 54.8 (dd, J = 7, 3 Hz, CH
of cod), 53.9 (d, J = 7 Hz, CH of cod), 41.1 (d, J = 5 Hz, CH2 of
cod), 35.4 (s, CH2 of cod), 36.1 (d, JCP = 6 Hz, CH2), 36.3
formation of a statistical mixture of 2b:2b-d3 :PhSC2H3 in a
1:1:1 ratio.
Reaction of [Ru(ꢁ2-C2H3OPh)(cod)(depe)] 2a with depe
(s, CH2 of cod), 33.2 (d, JCP = 8 Hz, SCH᎐CH ), 33.0 (dd,
A 5 mm NMR tube was charged first with a solid sample of 2a
(11.6 mg, 0.022 mmol) under a nitrogen atmosphere and C6D6
(0.5 cm3). Then, depe (0.01 cm3, 0.04 mmol) was added. 1H and
᎐
2
JCP = 12, 5 Hz, SCH᎐CH ), 29.9 (s, CH of cod), 27.0 (s, CH of
᎐
2
2
2
cod).
J. Chem. Soc., Dalton Trans., 2000, 2613–2625
2621
Planas, Jose Giner
