M.I. Bruce et al. / Journal of Organometallic Chemistry 690 (2005) 792–801
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4. Experimental
]Cp*}2 (4) (5%). H NMR: d 2.24 (s, 30H, Cp*), 6.43
(br, 2H, P2CH). 31P NMR: d ꢀ3.05 (s, P2CH).
4.1. General experimental conditions
4.5. [{Ru(dppm)Cp*}2(@C@CMeCMe@C@)](OTf)2
(5)
All reactions were carried out under dry, high purity
argon using standard Schlenk techniques. Common sol-
vents were dried, distilled under argon and degassed be-
fore use.
To a solution of 2 (500 mg, 0.38 mmol) in CH2Cl2 (25
mL) was added MeOTf (0.096 mL, 0.84 mmol, 2.2
equiv). The solution was stirred at r.t. for 3 h, gradually
changing in colour from orange to green. Diethyl ether
(50 mL) was added and the bright green product crystal-
lised. The solid was filtered and washed with THF and
diethyl ether to give [{Ru(dppm)Cp*}2(@C@CMeC-
Me@C@)](OTf)2 (5) (390 mg, 63%). Anal. Calc.
(C78H80F6O6P4Ru2S2): C, 57.92; H, 4.98; M (cation),
1320. Found: C, 58.01; H, 4.86%. IR (Nujol, cmꢀ1):
4.2. Instrumentation
Infrared spectra were obtained on a Bruker IFS28
FT-IR spectrometer. Spectra in CH2Cl2 were obtained
using a 0.5 mm path-length solution cell with NaCl win-
dows. Nujol mull spectra were obtained from samples
mounted between NaCl discs. NMR spectra were re-
corded on Bruker AM300WB or ACP300 (1H at
300.13 MHz, 13C at 75.47 MHz, 31P at 121.503 MHz)
instruments. Samples were dissolved in CDCl3, unless
otherwise stated, contained in 5 mm sample tubes.
Chemical shifts are given in ppm relative to internal tet-
1
m(C@C) 1626 m. H NMR (acetone-d6): d 0.06 (s, 6H,
2 · Me), 1.98 (s, 30H, Cp*), 4.82, 5.32 (2m, 2 · 2H,
CH2), 7.22–7.61 (m, 40H, Ph). 13C NMR (acetone-d6):
d 8.75 (s, Me), 12.37 (s, C5Me5), 45.77 [t, J(CP) 27 Hz,
CH2], 104.61 (s, C5Me5), 117.45 (s, C2), 129.96–136.81
(m, Ph), 352.20 [t, J(CP) 14 Hz, C1]. 31P NMR (ace-
tone-d6): d 2.00 (s, dppm). ES-mass spectrum (m/z):
1
ramethylsilane for H and 13C NMR spectra and exter-
nal H3PO4 for 31P NMR spectra. ES mass spectra: VG
Platform 2 or Finnigan LCQ. Solutions were directly in-
fused into the instrument. Chemical aids to ionisation
were used as required [23]. Cyclic voltammograms were
recorded using a PAR model 263 apparatus, a saturated
calomel electrode, and ferrocene as internal calibrant
([FeCp2]/[FeCp2]+ = +0.46 V). Elemental analyses were
performed at the Centre pour Microanalyses du CNRS,
Vernaison, France, and CMAS, Belmont, Australia.
1469, [M + OTf]+; 660, [M]2+
.
4.6. Ru{CCCH@CH(PPh2)2[Rucp*]}(dppm)Cp* (6)
To a suspension of 5 (70 mg, 0.04 mmol) in THF (10
mL) was added KOBut (19.4 mg, 0.17 mmol). The reac-
tion was left to stir at r.t. for 10 min before the solvent
was removed and the orange solid extracted into hexane.
The solution was filtered and concentrated under vac-
uum to give bright orange crystals identified as
Ru{C„CCH@CH(PPh2)2[RuCp*]}(dppm)Cp* (6) (44
mg, 78%). Anal. Calc. (C75H76P4Ru2): C, 69.11; H,
5.88; M, 1304. Found: C, 69.14; H, 5.91%. IR (Nujol,
cmꢀ1): m(C„C) 1950 w; m(C@C) 1713 m. 1H NMR (ben-
zene-d6): d 1.97 (s, 15H, Cp*), 1.99 [t, J(HP) 12 Hz, 3H,
Me], 2.22 (s, 15H, Cp*), 3.94, 4.25 (2m, 2 · 1H, CH2),
5.43 [t, J(HP) 4 Hz, 1H, PCHP], 6.78–7.73 (m, 40H,
Ph). 13C NMR (toluene-d8): d 11.42 (s, C8), 13.15 (s,
C10), 27.87 [t, J(CP) 7 Hz, C5], 29.94 (s, C31), 49.79
[t, J(CP) 22 Hz, C6], 72.54 [t, J(CP) 23 Hz, C3], 87.85
[t, J(CP) 2 Hz, C9], 91.28 [t, J(CP) 2 Hz, C7], 113.54
[t, J(CP) 11 Hz, C2], 116.84 [tt, J(CP) 25 Hz, J(CP) 5
Hz, C1], 126.30–139.10 (m, Ph), 203.24 (s, C4). 31P
NMR (benzene-d6): d 0.49 (s, P2CH), 19.05 (s, dppm).
ES-mass spectrum (m/z): 1336, [M + MeOH]+; 1305,
[M + H]+.
4.3. Reagents
Compounds 1, 2 and 8-Ru were prepared using the
methods previously reported [3b].
4.4. Treatment of
[{Ru(dppm)Cp*}2(@C@CHCH@C@)](PF6)2 (1)
with KOBut
To a solution of 1 (50 mg, 0.03 mmol) in THF (20
mL) was added KOBut (10.6 mg, 0.09 mmol). The reac-
tion mixture was left to stir at r.t. for 10 min before the
solvent was removed. The orange residue was extracted
into hexane and the solution filtered and concentrated
under vacuum to give a bright orange solid (40 mg),
identified by NMR as a mixture of three complexes:
1
{Ru(dppm)Cp*}2(l-C„CC„C) (2) (35%). H NMR:
d 1.90 (s, 30H, Cp*), 4.22 (m, 4H, CH2). 31P NMR: d
16.63
(s,
dppm);
Ru{C„CCH@CCH(P-
4.7. [{Ru(dppe)Cp*}2(@C@CHCH@C@)](OTf)2
(7-Ru/OTf)
1
Ph2)2[RuCp*]}(dppm)Cp* (3) (60%). H NMR: d 1.98
[t, J(HP) 2 Hz, 15H, Cp*], 2.07 [t, J(HP) 1 Hz, 15H,
Cp*], 2.11 (s, 1H, @CH), 3.85, 4.12 (m, 2H, CH2),
5.59 [t, J(HP) 4 Hz, 1H, P2CH]. 31P NMR: d ꢀ1.80 (s,
P2CH), 18.99 (s, dppm); {Ru[(PPh2)2CHC@CH–
To a solution of {Ru(dppe)Cp*}2(C„CC„C) (8-Ru)
(100 mg, 0.07 mmol) in CH2Cl2 (10 mL) was added
HOTf (0.015 mL, 0.17 mmol, 2.2 equiv). The reaction
Bruce, Michael I.
