Reactivity of {Ru(C5Me5)[η2-P, O -Ph2PCH2C(tBu)=O](CO)}[PF6]
analyses were performed by the “Service de Microanalyse du
CNRS” Solaize, France. Complex 1 was prepared as reported pre-
viously.[12]
NMR
(81.0 MHz,
CD2Cl2):
δ
=
37.2
(s)
ppm.
C38H46F6O3P2Ru·H2O (845.81): calcd. C 53.96, H 5.72, P 7.32;
found C 53.90, H 5.50, P 7.09.
{Ru[:C(Me)OMe](Cp*)[Ph2PCH2C(=O)tBu](CO)}[PF6] (2a):
A
{Ru(Cp*)[η2-C,P-:C(Me)OC(tBu)=CH–PPh2](CO)}[PF6] (3a):
A
solution of 1 (1.00 g, 1.44 mmol) in methanol (20 mL) was stirred
for 24 h under an atmosphere of ethyne at room temperature. The
resulting slurry was evaporated under vacuum, and the residue was
dissolved in dichloromethane (30 mL). The pale-yellow solution
was covered with diethyl ether (140 mL) to afford pale-yellow crys-
solution of 1 (2.02 g, 2.91 mmol) in dichloromethane (35 mL) was
stirred for 24 h under an atmosphere of ethyne at room tempera-
ture. The resulting brown solution was evaporated under vacuum,
and the residue was dissolved in dichloromethane (25 mL). Diethyl
ether (110 mL) was then added to obtain a solution that was kept
overnight in a refrigerator to produce pale-yellow crystals of 3a.
1
tals of 2a. Yield: 0.95 g, 88%. H NMR (200 MHz, CD2Cl2): δ =
4
1
1.05 (s, 9 H, CMe3), 1.66 (d, JP,H = 1.7 Hz, 15 H, C5Me5), 2.70
Yield: 1.04 g, 50%. H NMR (200.1 MHz, CD2Cl2): δ = 1.26 (s, 9
4
2
4
(d, JP,H = 0.9 Hz, 3 H, =CMe), 3.75 (dd, 2JH,H = 17.8 Hz, JP,H
=
H, CMe3), 1.81 (d, JP,H = 1.5 Hz, 15 H, C5Me5), 2.90 (s, 3 H,
7.1 Hz, 1 H, PCH2, Ha), 3.85 (dd, 2JH,H = 17.8 Hz, 2JP,H = 8.8 Hz,
1 H, PCH2, Hb), 4.32 (d, 5JP,H = 0.8 Hz, 3 H, OMe), 7.29–7.62 (m,
10 H, Ph) ppm. 13C{1H} NMR (50.3 MHz, CD2Cl2): δ = 9.8 (s,
C5Me5), 26.4 (s, CMe3), 40.3 (d, 1J = 35.1 Hz, PCH2), 43.7 (s, Me),
=CMe), 6.22 (d, JP,H = 5.0 Hz, 1 H, PCH=), 7.19–7.30 (m, 2 H,
2
Ph), 7.62–7.64 (m, 8 H, Ph) ppm. 13C{1H} NMR (50.3 MHz,
3
CD2Cl2): δ = 10.2 (s, C5Me5), 27.5 (s, CMe3), 38.3 (d, J = 5.8 Hz,
CMe3), 46.3 (s, =CMe), 98.4 (d, 1J = 60.5 Hz, PCH=), 105.1 (s,
45.7 (d, 3J = 2.1 Hz, CMe3), 65.4 (s, OMe), 101.9 (s, C5Me5), 129.3 C5Me5), 129.1 (part of d, Ph, ipso), 130.0 (d, 2J = 10.9 Hz, Ph,
(d, 2J = 11.0 Hz, Ph, ortho), 129.3 (d, 2J = 9.4 Hz, Ph, ortho), 129.8 ortho), 130.0 (d, 2J = 11.0 Hz, Ph, ortho, likely overlapping the sec-
1
4
3
(d, J = 57.7 Hz, Ph, ipso), 131.5 (d, J = 2.4 Hz, Ph, para), 131.9
ond part of d, Ph, ipso), 131.2 (d, J = 11.1 Hz, Ph, meta), 131.2
3
4
1
4
(d, J = 10.9 Hz, Ph, meta), 132.0 (d, J = 2.1 Hz, Ph, para), 132.7
(d, J = 60.0 Hz, Ph, ipso), 132.4 (d, J = 2.5 Hz, Ph, para), 132.9
(d, 1J = 48.9 Hz, Ph, ipso), 132.9 (d, 3J = 11.0 Hz, Ph, meta), 205.0 (d, partially overlapped, Ph, meta), 133.0 (d, partially overlapped,
2
2
2
2
(d, J = 15.9 Hz, CϵO), 209.8 (d, J = 6.1 Hz, C=O), 318.8 (d, J
Ph, para), 177.2 (s, OC=CH), 202.1 (d, J = 15.0 Hz, CϵO), 312.3
= 12.3 Hz, Ru=C) ppm. 31P{1H} NMR (81.0 MHz, CD2Cl2): δ = (d, 2J = 15.7 Hz, Ru=C) ppm. 31P{1H} NMR (81.0 MHz, CD2Cl2):
37.2 (s) ppm. C32H42F6O3P2Ru (751.69): calcd. C 51.13, H 5.63, P
8.24; found C 51.12, H 5.62, P 8.13.
δ = 37.2 (s) ppm. C31H38F6O2P2Ru (719.65): calcd. C 51.74, H 5.32,
P 8.61; found C 51.63, H 5.27, P 8.60.
{Ru[:C(CH2tBu)OMe](Cp*)[Ph2PCH2C(=O)tBu](CO)}[PF6] (2b):
To a solution of 1 (2.03 g, 2.93 mmol) in methanol (35 mL) was
added 3,3-dimethyl-1-butyne (1.0 mL, 8.12 mmol, excess), and the
mixture was stirred for 24 h at room temperature. The resulting
slurry was evaporated under vacuum and the residue was dissolved
in dichloromethane (30 mL). The yellow solution was covered with
diethyl ether (120 mL) to afford yellow crystals of 2b. Yield: 1.69 g,
{Ru(Cp*)[η2-C,P-:C(CH2Ph)OC(tBu)=CH–PPh2](CO)}[PF6] (3c):
To a solution of 1 (3.01 g, 4.34 mmol) in dichloromethane (40 mL)
was added phenylacetylene (1.00 mL, 9.11 mmol, excess), and this
mixture was stirred for 5 d at room temperature. The resulting dark
solution was evaporated to leave a sticky residue. On standing for
5 d, yellow crystals formed. Methanol (15 mL) was added, and the
mixture was shaken for 5 min to obtain a crystalline yellow precipi-
tate that was collected by filtration, then washed with diethyl ether
(30 mL) and dried under vacuum. Analysis of the product by 1H
NMR spectroscopy disclosed a mixture of 3c (83%) and 5c (17%).
1
71%. H NMR (200 MHz, CD2Cl2): δ = 1.07 (br. s, 18 H, CMe3),
4
1.69 (d, JP,H = 1.7 Hz, 15 H, C5Me5), 2.73–2.96 and 3.73–3.77 (2
br. m, 4 H, PCH2 and tBuCH2), 4.49 (s, 3 H, OMe), 7.32–7.42 (m,
4 H, Ph), 7.52–7.63 (m, 6 H, Ph) ppm. 13C{1H} NMR (50.3 MHz, Overall yield: 2.28 g, 66%. Data for 3c: 1H NMR (200.1 MHz,
4
CD2Cl2): δ = 10.3 (s, C5Me5), 26.8 (s, CMe3), 31.4 (v. br. s, CMe3), CD2Cl2): δ = 0.90 (s, 9 H, CMe3), 1.86 (d, JP,H = 1.5 Hz, 15 H,
1
3
2
2
36.9 (v. br. s, CH2tBu), 40.9 (d, J = 34.4 Hz, PCH2), 46.1 (d, J = C5Me5), 4.31 (d, JH,H = 17.0 Hz, 1 H, CH2Ph), 4.59 (d, JH,H
=
2
2
1.9 Hz, CMe3), 68.5 (s, OMe), 102.1 (br. s, C5Me5), 129.7 (d, J =
17.0 Hz, 1 H, CH2Ph), 6.17 (d, JP,H = 5.1 Hz, 1 H, PCH=), 6.99–
7.04 (m, 2 H, Ph), 7.26–7.70 (m, 13 H, Ph) ppm. 13C{1H} NMR
(50.3 MHz, CD2Cl2): δ = 10.3 (s, C5Me5), 27.1 (s, CMe3), 38.3 (d,
3J = 6.9 Hz, CMe3), 65.2 (s, CH2Ph), 98.3 (d, 1J = 60.4 Hz, PCH=),
105.3 (d, 2J = 1.7 Hz, C5Me5), 127.8 (s, Ph, para), 129.1 (s, Ph,
ortho or meta), 129.6 (s, Ph, ortho or meta), 130.1 (d, 2J = 11.6 Hz,
10.4 Hz, Ph, ortho), 129.8 (br. d, 2J = 10.4 Hz, Ph, ortho), 131.9
4
4
(part of d, Ph, ipso), 132.2 (d, J = 2.5 Hz, Ph, para), 132.3 (d, J
3
3
= 1.9 Hz, Ph, para), 132.7 (d, J = 12.3 Hz, Ph, meta), 132.9 (d, J
= 10.9 Hz, Ph, meta), 206.8 (br. s, CϵO), 210.0 (s, C=O), 326.4 (br.
s, Ru=C) ppm. 31P{1H} NMR (81.0 MHz, CD2Cl2): δ = 35.34 (br.
s) ppm. C36H50F6O3P2Ru (807.80): calcd. C 53.53, H 6.24, P 7.67; PhP, ortho), 130.1 (d, 2J = 11.6 Hz, PhP, ortho), 130.7 (d, 1J =
1
3
found C 53.54, H 6.29, P 7.25.
57.7 Hz, PhP, ipso), 131.1 (d, J = 60.2 Hz, PhP, ipso), 131.3 (d, J
4
= 11.2 Hz, PhP, meta), 132.5 (d, J = 2.3 Hz, PhP, para), 133.1 (d,
{Ru[:C(CH2Ph)OMe](Cp*)[Ph2PCH2C(=O)tBu](CO)}[PF6] (2c):
Using phenylacetylene, the procedure detailed for 2b was appropri-
ate to prepare 2c in 86% yield as shiny yellow crystals that retained
3J = 13.5 Hz, PhP, meta), 133.2 (d, J = 2.5 Hz, PhP, para), 135.2
4
(s, Ph, ipso), 177.3 (d, 2J = 1.7 Hz, OCtBu), 202.1 (d, 2J = 14.0 Hz,
CϵO), 310.6 (d, 2J = 16.0 Hz, Ru=C) ppm. 31P{1H} NMR
(81.0 MHz, CD2Cl2): δ = 36.8 (s) ppm.
1
1 mol of water per Ru. H NMR (200.1 MHz, CD2Cl2): δ = 1.06
(s, 9 H, CMe3), 1.56 (d, 4JP,H = 1.4 Hz, 15 H, C5Me5), 3.84 (d, 2JP,H
= 7.7 Hz, 2 H, PCH2), 4.08 (d, 2JH,H = 13.6 Hz, 1 H, CH2Ph), 4.27
Ru(CϵCtBu)(Cp*)[Ph2PCH2C(=O)tBu](CO) (4): A mixture con-
sisting of 1 (2.00 g, 2.88 mmol), KHCO3 (1.00 g, 10.0 mmol), tert-
butylacetylene (1.20 mL, 9.74 mmol, excess) and dichloromethane
(35 mL) was stirred for 3 d at room temperature. The slurry was
then evaporated to dryness to afford a solid that was extracted with
dichloromethane (30 mL). The solution was filtered, and the yellow
2
(d, JH,H = 13.7 Hz, 1 H, CH2Ph), 4.55 (s, 3 H, OMe), 7.24–7.29
(m, 2 H, Ph), 7.39–7.64 (m, 13 H, Ph) ppm. 13C{1H} NMR
(50.3 MHz, CD2Cl2): δ = 9.7 (s, C5Me5), 26.3 (s, CMe3), 40.5 (d,
1J = 34.1 Hz, PCH2), 45.8 (s, CMe3), 60.7 (br. s, CH2Ph), 67.4 (s,
OMe), 102.4 (s, C5Me5), 128.4 (s, CH2Ph, para), 129.4 (d, 2J =
10.6 Hz, PPh2, ortho), 129.7 (s, CH2Ph), 130.1 (s, CH2Ph), 131.6 filtrate was evaporated under vacuum to yield crude product 4,
(d, 1J = 57.8 Hz, PPh2, ipso), 131.9 (d, 4J = 2.7 Hz, PPh, para),
which was dissolved in hexane (5 mL). A light-yellow crystalline
4
131.9 (s, CH2Ph, ipso), 132.0 (d, J = 2.8 Hz, PPh, para), 132.6 (d, solid was obtained upon cooling the solution in a refrigerator.
2
1
3J = 9.8 Hz, PPh2, meta), 205.5 (d, J = 17.2 Hz, CϵO), 209.7 (d, Yield: 1.50 g, 83%. H NMR (200.1 MHz, CD2Cl2): δ = 0.91 (s, 9
2
4
2J = 6.1 Hz, C=O), 317.6 (d, J = 12.3 Hz, Ru=C) ppm. 31P{1H}
H, CMe3), 1.37 (s, 9 H, CMe3), 1.63 (d, JP,H = 1.8 Hz, 15 H,
Eur. J. Inorg. Chem. 2009, 4308–4313
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4311