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Synthesis of Complexes
2 and 4: To a suspension of [RuCl2(p-cymene)]2 (0.72
g, 1.17 mmol) in toluene (45 mL), the phosphine PCy3 (1.32
g, 4.7 mmol) or PPh3 (1.23 g, 4.7 mmol) was added and
stirred at r.t. The mixture instantly changed into a reddish brown
solution. Me3SiCCH (3.34 mL,
23.5 mmol) was added and the solution was stirred for 1 h at r.t.
The solution instantly darkened to a dark red solution. After 1
h the temperature was gradually risen to 60 °C
and stirred during one night. The analytical pure compound was obtained
(65% yield) after washing the crude product with methanol.
Cl2Ru{=C=C(H)SiMe3}(PPh3)2(2): 1H NMR (299.89
MHz, C6D6, 25 °C): δ = 7.82-7.64
and 7.00-6.65 (each m, 30 H, PPh3), 0.33 (s,
9 H, SiCH
3), 0.01 (dt, J
(RuH) = 2.1
Hz, J
(PH) = 2.5
Hz, 1 H, =CHSiMe3).
13C
NMR (75.41 MHz, C6D6, 25 °C): δ = 279.33
(dt, J
(RuH) = 57.0
Hz, J
(PC) = 15.4
Hz, Ru=C=C), 86.45
(dt, J
(RuH) = 15.7
Hz, J
(PC) = 5.1
Hz, Ru=C=C), 150.16
(s, C1 of PPh), 129.77, 128.00, 126.87 (s, PPh). 31P
NMR {1H} (121.40 MHz, C6D6,
25 °C, ref. H3PO4): δ = 26.3
(s). IR (KBr): ν = 1625 (C=C) cm-1.
Anal. Calcd for C41H40Cl2P2SiRu:
C, 61.96; H, 5.07. Found: C, 62.30; H, 5.82. Cl2Ru{=C=C(H)SiMe3}(PCy3)2(4): 1H NMR (299.89 MHz, C6D6,
25 °C): δ = 2.68-2.59,
2.13-1.97, 1.89-1.64, 1.26-1.16 (each
m, 66 H, PCy3), 0.29 (s, 9 H, SiCH
3),
0.023 (dt, J
(RuH) = 1.9
Hz, J
(PH) = 2.8
Hz, 1 H, =CHSiMe3). 13C NMR
(75.41 MHz, C6D6, 25 °C): δ = 274.30
(dt, J
(RuH) = 57.2
Hz, J
(PC) = 15
Hz, Ru=C=C), 81.20
(dt, J
(RuH) = 16
Hz, J
(PC) = 5
Hz, Ru=C=C), 35.46
(pseudo triplet, J = 8.7
Hz, C1 of PCy), 30.14 (s, C3,5 of
PCy), 27.83 (pseudo triplet, J = 4.2
Hz, C2,6 of PCy), 26.35 (s, C4 of
Pcy). 31P NMR {1H} (121.40
MHz, C6D6, 25 °C, ref. H3PO4): δ = 31.50
(s). IR (KBr): ν = 1630 (C=C) cm-1.
Anal. Calcd for C41H76Cl2P2SiRu:
C, 59.26; H, 9.58. Found: C, 59.52; H, 10.10.
15a
Morgan JP.
Grubbs RH.
Org. Lett.
2000,
2:
3153
15b
Louie J.
Grubbs RH.
Angew. Chem. Int.
Ed.
2001,
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247
16
A Typical Procedure
for the Preparation of Complex 6 is as follows. A solution
(0.1 M in THF) of the 4,5-dihydroimidazol-2-ylideen tetrafluoro-borate
salt (300 ml) (STREM), a magnetic stirring bar and toluene (1 mL)
were added to a glass vessel. t-BuOK
was added (30 µL 1 M in Et2O, Aldrich) to the
rapidly stirred suspension at r.t., resulting in the immediate dissolution
of the salt to form a light yellow solution. After 5 min, a 0.1
M solution of the vinylidene (3 or 4, 250 µL) or alkylidene [Cl2(PCy3)2Ru
(= CHPh)] complex
in toluene were added via cannula. The mixture was heated to 70 °C
for 1 h and subsequently cooled to r.t. Complex 6: 1H
NMR (299.89 MHz, C6D6, 25 °C):
δ = 7.03-6.96
(br, 2 H, Mes), 6.92-6.86 (br, 2 H, Mes), 3.49 (s, 4 H,
imidazolium), 2.44-2.10, 1.99-1.84 (br,18 H, Mes), 2.12
(m, 3 H, C1 PCy3), 1.55-1.52,
1.39, 1.02-0.96 (m, 32 H, PCy3) 0.05 (s, 9 H,
SiCH
3), -0.15 (dt, J
(RuH) = 1.9
Hz, J
(PH) = 2.8
Hz, 1 H, =CHSiMe3). 13C
NMR (75.41 MHz, C6D6, 25 °C): δ = 267.27
(dt, J
(RuH) = 56.8
Hz, J
(PC) = 15
Hz, Ru=C=C), 194.46
(s, J
(CP) = 80
Hz, Ru-CNN), 144.82, 141.00, 137.64, 134.95, 131.93 (all s, Mes),
129.01 (d, J
(CH) = 150
Hz, Mes), 128.82 (d, J
(CH) = 130Hz,
Mes), 71.05 (dt, J
(RuH) = 15
Hz, J
(PC) = 5.5
Hz, Ru= C=C),
31.30 (pseudo triplet, J = 9
Hz, C1 of PCy3), 29.96 (s, C3,5 of
PCy), 27.87 (pseudo triplet, J = 4
Hz, C2,6 of PCy3), 26.36 (s, C4 of
PCy3) 21.96, 21.13, 19.54, 18.61 (all s, Mes). 31P
NMR {1H} (121.40 MHz, C6D6,
25 °C, ref. H3PO4): δ = 28.03
(s). IR (KBr): ν = 1634 (C = C)
cm-1. Anal. Calcd for C44H69N2Cl2PSiRu:
C, 61.66; H, 8.11; N, 3.27. Found: C, 62.98; H, 9.23; N, 4.03.
17a
Baratta W.
Herrmann WA.
Rigu P.
Schwarz J.
J. Organomet.
Chem.
2000,
593:
489
17b
Yi CS.
Liu N.
Synlett
1999,
3:
281
18
Melis K.
Opstal T.
Verpoort F.
Eur.
J. Org. Chem.
2002,
3779
