C. Lexer et al. / Journal of Organometallic Chemistry 696 (2011) 2466e2470
2469
{1H} NMR (
d
, 22 C, CDCl
ꢀ
, 125 MHz): 283.8 (1C, Ru]CH), 216.7 (1C,
purification. Monomers 3 and 4 were prepared according to the
literature procedures [20]. CH Cl was distilled over CaH and
3
2
2
2
NHC), 142.3, 140.2, 139.8, 138.5, 138.0, 136.8 (6C, Cq), 136.0 (1C, Ct),
degassed with argon. All experiments were carried out under inert
atmosphere. Gel permeation chromatography (GPC) was used to
determine molecular weights and the polydispersity index (PDI) of
polymer samples with THF as the solvent with the following
arrangement: a Merck Hitachi L6000 pump, separation columns
135.6, 134.8,132.2 (3C, Cq), 131.1, 131.0, 129.8, 129.7, 128.5, 128.2,
2
127.8 (7C, Ct), 120.0 (1C, Cq), 51.2, 51.1 (2C, N-CH ), 21.4, 21.0, 20.1,
18.4, 18.3, 16.3 (b, MesCH ).
3
4.4. General procedure for the RCM of DEDAM
from Polymer Standards Service [8 ꢂ 300-mm STV 5-
m
m-grade size
6
4
3
(
10 , 10 , and 10 Ǻ)], a refractive-index detector from Wyatt
In a Schlenk-tube, a mixture of 2 (0.5 mg, 1 mol%) and 5 (20 mg,
Technology, a model Optilab DSP interferometric refractometer,
and polystyrene standards purchased from Polymer Standard
0.08 mmol) was stirred in dry solvent (10 mL). For solvent and
reaction conditions, see Table 1. Purification was done by flash
chromatography (SiO
, Cy:EA ¼ 2:1). The obtained product was
evaporated to dryness and dried under vacuum.
1
Service was used for calibration. H NMR spectra were recorded on
2
a Varian INOVA 500-MHz spectrometer 2 versus SiMe
4
as a stan-
dard at 500 MHz; 13C{ H} NMR spectra were recorded at 125 MHz.
The solvent residual peak of CDCl was used for referencing the
1
1
ꢀ
RCM product (6): H NMR (
d
, 20 C, CDCl
3
, 500 MHz): 5.60 (s,
3
3
,4
2,5
2
H, cp ), 4.19 (q, 4H, OCH CH ), 3.00 (s, 4H, cp ), 1.24 (t, 6H,
2 3
NMR spectra to 7.26 and 77.16 ppm, respectively. The relaxation
13
ꢀ
3
(d, 20 C, CDCl , 500 MHz): 172.5 (2C,
OCH
2
CH
3
).
C
NMR
1
delay for H NMR spectra was set to 5 s. DSC measurements were
3
,4
1
COOCH
1.1 (2C, cp ), 14.3 (2C, OCH
2
CH
3
), 128.0 (2C, cp ), 61.8 (2C, OCH CH ), 59.0 (1C, cp ),
2 3
made with a Perkin Elmer Pyris Diamond Differential Scanning
Calorimeter equipped with a Perkin Elmer CCA7 cooling system
using liquid nitrogen. A nitrogen flow of 20 mL/min and a heating
2
,5
4
2
CH
Side product (7): H NMR ( , 20 C, CDCl
), 4.17 (q, 4H, OCH CH ), 3.05, 3.02 (1H, cp ), 2.95,
3
).
1
ꢀ
d
3
, 500 MHz): 4.89, 4.77
2
(
2
2 ꢂ s, 2H, CH
2
2
4
3
ꢀ
rate of 10 C/min were used.
2
5
.91 (1H, cp ), 2.60e2.50 (m,1H, cp ), 2.16,1.74 (2H, cp ),1.23 (t, 6H,
13
ꢀ
OCH
2
CH
3
), 1.10 (d, 3H, CHCH
CH
CH
), 13.3 (2C, COOCH
3
). C NMR (
d
, 20 C, CDCl
), 104.6 (1C, C]
), 57.3 (1C, cp ), 41.3, 39.7, 36.5 (3C,
CH ).
3
, 500 MHz):
4.2. Synthesis of diphenyl-(2-vinylphenyl)-phosphine (1)
1
71.2, 171.1 (2C, COOCH
2
3
), 152.6 (1C, C]CH
2
1
CH ), 60.7 (2C, COOCH
2
2
3
Magnesia (0.66 g, 0.027 mol) and 1-bromo-2-vinylbenzene
2
,4,5
cp
), 17.2 (1C, CHCH
3
2
3
(
5.00 g, 0.027 mol) were mixed in THF (10 mL) under argon atmo-
sphere. The reaction mixture was heated using a heatgun until the
reaction started. Subsequently the mixture was cooled with an ice
bathand stirreduntil allMgwasdissolved. Chlorodiphenylphosphine
4.5. General procedure for the RCM of Tos-DAA
(
4.82 g, 0.021 mol), dissolved in6 mLofTHFwasslowlyadded tokeep
In a Schlenk-tube, a mixture of catalysts 2 (0.5 mg,1 mol%) and 8
(20 mg, 0.08 mmol) was stirred in dry solvent (10 mL). For solvent
and reaction conditions, see Table 1. Purification was done by flash
the solution gently boiling. The reaction was stirred for 1 h at reflux
and then poured into 500 mL of water and ice. The product was
extracted with Et
done by flash chromatography (SiO
product was evaporated to dryness under reduced pressure. Yield:
2
O and precipitated in n-pentanes. Purification was
chromatography (SiO
2
, Cy:EE ¼ 2:1). The obtained product was
2
, CH Cl
2
2
:n-pentane ¼ 1:1). The
evaporated to dryness and dried under vacuum.
1
ꢀ
RCM product (9): H NMR (d, 20 C, CDCl , 500 MHz): 7.65 (d,
3
3
,5
2,6
3,4
2,5
3
.46 g (55%)
2H, ph ), 7.28 (d, 2H, ph ), 5.60 (s, 2H, cp ), 4.09 (s, 4H, cp ),
1
3
ꢀ
Anal. calcd. for: C20
H
17P (MW: 288.32): C, 83.31; H, 5.94. Found:
2.38 (s, 1H, eCH
3
). C NMR (
d
, 20 C, CDCl
3
, 125 MHz): 140.9 (1C,
1
ꢀ
4
1
3,5
2,6
C, 83.72; H, 5.99. H NMR (
d
, 20 C, CDCl
3
, 500 MHz): 7.62 (m, 1H,
ph ), 136.3 (1C, ph ), 129.5 (2C, ph ), 125.9, 125.4 (4C, ph
,
3
4
Ph ), 7.35, 7.29 (m, 12H, Ph, eCHeCH
2
), 7.18 (t, 1H, Ph ), 6.83 (m, 1H,
CH
2
CH]CHCH
Side product (10): H NMR (
2
), 46.9 (2C, N-CH
2
), 20.9 (1C, ph-CH
3
).
5
3
2
1
ꢀ
Ph ), 5.65 (dd, 1H, JHHtrans ¼ 17.5 Hz, JHH ¼ 1.0 Hz, CH
2
]CH), 5.24
d
, 20 C, CDCl
3
, 500 MHz): 7.70, 7.32
), 4.11, 3.95, 3.80,
(
2
dd, 1H, 3
J
HHcis ¼ 10.5 Hz, CH
2
]CH). P{ H} NMR (
31
1
d
, 22 C, CDCl
ꢀ
3
,
(2 ꢂ d, 2 ꢂ 2H, ph
2,3,5,6
), 4.90, 4.85 (2 ꢂ s, 2H, CH
2
13
1
ꢀ
1,2,5
4
00 MHz): ꢃ15.4. C{ H} NMR (
d
, 20 C, CDCl
3
, 125 MHz): 142.6
3.73, 3.57 (5H, cp
), 2.43 (s, 4H, ph-CH
3
, cp ), 1.04 (d, 3H, CHCH
3
4
).
1
13
ꢀ
1
(
1C,
J
CP ¼ 21.9 Hz, C1), 136.6 (1C, JCP ¼ 10.0 Hz, C6), 135.6 (2C,
C NMR (
d
, 20 C, CDCl
3
, 125 MHz): 149.4 (1C, cp ), 143.7 (1C, ph ),
1
0
00
2
1
3,5
2,6
J
CP ¼ 23.9 Hz, C1 ,1 ), 135.3 (1C,
J
CP ¼ 13.8 Hz, C2), 134.2 (4C,
133.0 (1C, ph ), 129.8 (2C, ph ), 127.9 (2C, ph ), 106.1 (1C, CCH
55.2, 52.3 (2C, cp ), 37.6 (1C, cp ), 21.7 (1C, ph-CH
CHCH ).
2
),
2JCP ¼ 19.5 Hz, C2 ,2 ,6 ,6 ), 133.4, 129.2, 128.1, (3C,C3,4,5), 129.0
0
00
0
00
2,5
4
), 16.2 (1C,
3
0
00
3
0
00
0
00
(
2C, C4 ,4 ), 128.7 (4C,
J
CP ¼ 7.1 Hz, C3 ,3 ,5 ,5 ), 125.8 (1C,
3
3
4
J
CP ¼ 4.75 Hz, CH]CH
2
), 116.3 (1C, JCP ¼ 2.4 Hz, CH
2
]CH).
4.6. General polymerization procedure in NMR-tube
4.3. Preparation of (SPY-5-34)-dichloro-(
k
2(C,P)-diphenyl-(2-vinyl-
benzylidene)-phosphine)-(1,3-bis(2,4,6-trimethylphenyl) 4,5-
dihydro-imidazol-2-ylidene)-ruthenium (2)
Monomer 3 (100 mg, 0.5 mmol) was dissolved in CDCl
subsequently 2 (1 mg, 0.002 mmol), dissolved in CDCl , was added.
): 5.94e5.14 (bm, 2H, CH]
3
and
3
1
ꢀ
H NMR (
d
, 20 C, 500 MHz, CDCl
CH ), 3.40e2.57 (bm, 4H, cp
.14e1.77 (bm, 1H, cp ), 1.66e1.37 (bm, 1H, cp ), 1.32e1.14 (bm, 6H,
3
2 2
To a solution of 1 (50 mg, 0.42 mmol) in CH Cl (6 mL) G3
1,2,3,4
CH), 4.32e3.98 (bm, 4H, CH
2
3
),
(
148 mg, 0.20 mmol) was added and the reaction mixture was
5
5
2
ꢀ
stirred at 25 C for 4 h. Afterwards, the mixture was evaporated to
13
ꢀ
CH
2
CH
3
). C NMR (
d
, 20 C, 125 MHz, CDCl
CH ), 53.1e51.9 (CHeCOO),
, CHeCH]), 15.0e14.0 (CH CH ).
3
): 174.1e173.1 (C]O),
2 2 2
dryness and the residue was redissolved in CH Cl /Et O. Upon
1
33.5e130.0 (CH]CH), 60.8e60.6 (CH
2
3
addition of heptanes a brown precipitate formed which was sepa-
rated by filtration washed with heptanes and dried in vacuum.
Yield: 92 mg (60%)
47.2e39.0 (CH
2
2
3
Anal. calcd. for: C40
Found: C, 63.72; H, 5.43. H NMR (
H
41Cl
2
N
2
PRu (MW: 752.72): C, 63.83; H, 5.49.
Acknowledgment
1
ꢀ
d
, 22 C, CDCl
3
, 500 MHz): 17.06
(
1
4
1
s, 1H, Ru]CH), 7.78, 7.56, 7.47, 7.40, 7.35, 7.19, 7.16, 7.11, 6.70 (vt,
Financial support by the Institute for Chemistry and Technology
of Materials of the Graz University of Technology and the Central
Polymer Laboratories (NAWI Graz) and the Israel Science Founda-
tion (54/09) is gratefully acknowledged.
0 0
,3 ,5,5
3
4H, aromatic signals), 7.00, 6.93, 6.84, 5.91 (bs, 4H, Mes
),
.26, 4.04, 3.96 (bm, 4H, N-CH
2
), 2.77, 2.71, 2.38, 2.31, 2.27, 2.20 (bs,
31
1
ꢀ
13
8H, MesCH
3
). P{ H} NMR (
d
, 22 C, CDCl
3
, 200 MHz): 57.8.
C