intermediate as that in the reaction of 1a followed by a further
addition of Me3SiN3. The reaction of 1c containing a vinyl
substituent on the cyclopropenyl ring with Me3SiN3 gave the
organic product 11, which contains a five-membered triazole
ring. Characterization of these products has led to a better
understanding of the mechanism of these reactions. The
reaction can be explained in terms of combined effects of
the nucleophilic sp3 carbon of the cyclopropenyl ring and the
electrophilic nature of the Me3Si group.
429.1 (Mϩ Ϫ PF6, PPh3, NCCH(Ph)CH2Ph). IR (KBr): 2254
cmϪ1. Anal. Calc. for C56H48F6NP3Ru: C, 64.49; H, 4.64; N,
1.34. Found: C, 64.52; H, 4.93; N, 1.54%.
Synthesis of [Ru]N4CCH(Ph)CH2CN 6
To a solution of complex 1b (0.51 g, 0.60 mmol) in THF (20
mL), Me3SiN3 (0.50 ml, 3.77 mmol) was added. After 3 h the
mixture was concentrated to ca. 5 mL, and slowly added to 60
mL of a stirring hexane. The yellow precipitate thus formed was
filtered off, and washed with hexane. The product was recrystal-
lized from acetone–hexane (1 : 4) and identified as 6 (0.45 g,
Experimental
1
85%). Spectroscopic data for 6: H NMR (C6D6): δ 7.59–6.81
General procedures
(m, 35H, Ph); 4.45 (dd, 1H, CH, JH–H = 7.4, 7.7 Hz); 4.29 (s, 5H,
Cp); 2.66, 2.44 (dd, 2H, CH2, JH–H = 16.6, 7.4, 7.7 Hz). 31P
NMR (CDCl3): δ 43.8, 41.6 (dd, JP–P = 38.9 Hz). 13C NMR
(CDCl3): δ 164.1 (NCN); 140.2 (Cipso of Ph); 138.3–127.1 (Ph);
118.6 (CN); 83.1 (Cp); 39.9 (CH); 23.5 (CH2). MS (FAB): m/z
889.2 (Mϩ, Ru = 102), 691 (Mϩ Ϫ N4CCH(Ph)CH2CN), 429.1
(Mϩ Ϫ PPh3; N4CCH(Ph)CH2CN). Anal. Calc. for C51H43N5-
P2Ru: C, 68.91; H, 4.88; N, 7.88. Found: C, 68.84; H, 4.84; N,
7.87%.
All manipulations were performed under nitrogen using
vacuum-line, dry box, and standard Schlenk techniques.
CH3CN and CH2Cl2 were distilled from CaH2 and diethyl
ether and THF from Na/ketyl. All other solvents and reagents
were of reagent grade and were used without further purifi-
cation. NMR spectra were recorded on Bruker DMX-500,
AM-300 and AC-200 FT-NMR spectrometers at room
temperature (unless stated otherwise) and are reported in units
of δ with residual protons in the solvent as standard (CDCl3,
δ 7.24; C6D6, δ 7.15; (CD3)2CO, δ 2.04). FAB mass spectra were
recorded on a JEOL SX-102A spectrometer. Complexes
Synthesis of [Ru]N4CCD(Ph)CDHCN (6-D)
To a solution of complex 1b (0.10 g, 0.12 mmol) and D2O
(12.96 µL, 0.72 mmol) in THF (10 mL) was added Me3SiN3
(0.10 mL, 0.75 mmol). After stirring for 4 h, the mixture was
concentrated to ca. 3 mL, and slowly added to 30 mL of stirring
hexane. The yellow precipitate thus formed was filtered off, and
washed with hexane. The major product was identified as 6-D
[Ru]–C᎐C(Ph)CHR ([Ru] = (η5-C H )(PPh ) Ru, R = Ph, 1a;
᎐
5
5
3 2
R = CN, 1b; R = CH᎐CH , 1c)4 were prepared following the
᎐
2
method reported in the literature. Elemental analyses and X-ray
diffraction studies were carried out at the Regional Center
of Analytical Instrument located at the National Taiwan
University.
1
(0.08 g, 80%). Spectroscopic data for 6-D: H NMR (CDCl3):
δ 7.78–7.02 (m, Ph, 35H), 4.30 (s, 5H, Cp); 2.58, 2.51 (two s, 1H,
CH, diastereomers). 31P NMR: δ 43.7, 41.4 (JP–P = 37.9 Hz). MS
(FAB): m/z 891.2 (Mϩ), 691 (Mϩ Ϫ N4CCD(Ph) Ϫ CDHCN),
429.1 (Mϩ Ϫ PPh3, N4CCD(Ph)CDHCN).
Reaction of 1a with Me3SiN3
To a solution of complex 1a (0.21 g, 0.23 mmol) in THF (20 ml)
was added Me3SiN3 (0.18 mL, 1.34 mmol) and the mixture was
stirred at room temperature for 7 h. Then the resulting orange
solution was dried in vacuo. The residue was extracted with
hexane and the residual solid was further washed with water to
give [Ru]N3 2 (0.14 g, 73% yield). The hexane extract was con-
centrated and was then eluted with diethyl ether on a silica gel
packed column and the solvent of the band containing the
organic compound was removed on a rotary evaporator to give
NCCH(Ph)CH2Ph 3 (0.046 g, 64% yield). Spectroscopic data
for 2: 1H NMR (CDCl3): δ 7.68–7.09 (m, 30H, Ph); 4.19 (s, 5H,
Cp). 31P NMR (CDCl3): δ 41.6. 13C NMR (CDCl3): δ 138.4–
127.5 (Ph); 81.3 (Cp). MS (FAB): m/z 733 (Mϩ), 705 (Mϩ Ϫ N2);
691 (Mϩ Ϫ N3). Anal. Calc. for C41H35N3P2Ru: C, 67.20; H,
4.81; N, 5.73. Found: C, 67.12; H, 4.77; N, 5.70%. Spectroscopic
Protonation of 6 with HCl
The reaction was carried out in a NMR tube. To a solution of
complex 6 (20 mg, 0.022 mmol) in CDCl3 prepared under N2, 5
µL of HCl (1 M in H2O) was added. The reaction completed
immediately and the color changed from yellow to green. The
solvent and HCl were removed in vacuo over 5 h at 60 ЊC. The
green product was washed with hexane, dried in vacuo and iden-
tified as {[Ru]–N4HCCH(Ph)CH2CN}Cl 9 (19 mg, 90% yield).
1
Spectroscopic data for 9: H NMR (CDCl3): δ 7.76–6.85 (m,
5H, Ph); 4.76 (t, 1H, CH, JH–H = 7.5 Hz); 4.34 (s, 5H, Cp); 2.83
(d, 2H, CH2, JH–H = 7.5 Hz). 31P NMR (CDCl3): δ 42.2, 42.4
(AB, JP–P = 36.2 Hz). MS (FAB): m/z 890.1 (Mϩ Ϫ Cl); 691.0
(Mϩ Ϫ Cl, N4HCCH(Ph)CH2CN).
1
data for 3: H NMR (CDCl3): δ 7.43–7.09 (m, 10H, Ph); 3.98
(dd, 1H, CH, JH–H = 8.4, 6.7 Hz); 3.17, 3.11 (dd, 2H, CH2, JH–H
= 8.4, 6.7, 13.7 Hz). High resolution MS: calc. for C15H13N: m/z
207.1048, found: 207.1050.
Reaction of complex 6 with CH3I
To a solution of complex 6 (22 mg, 0.024 mmol) in CDCl3
prepared under N2 in a NMR tube, 10 µL of CH3I was added.
The reaction was carried out at 50 ЊC for 10 h, and the color
changed from yellow to red. Then the solvent and excess of
CH3I were removed in vacuo. The organic product was
extracted with diethyl ether, and passed through a silica
column. A 1 : 1 diethyl ether–hexane solution eluted the
organometallic compound, [Ru]–I and MeOH eluted the
organic product identified as CH3N4CCH(Ph)CH2CN 10. Spec-
Preparation of {[Ru]NCCH(Ph)CH2Ph}PF6 5a
To a solution of complex 1a (0.45 g, 0.51 mmol) in THF (20
mL), Me3SiN3 (0.4 mL, 3.02 mmol) was added. The reaction
mixture turned orange in 2 h and starting material disappeared
as indicated by the 31P NMR spectrum. Then NH4PF6 (0.1 g,
0.6 mmol) was added and the solution stirred at 0 ЊC for 1 h.
The mixture was filtered through Celite, and the filtrate concen-
trated to ca. 5 mL at reduced pressure. Addition of hexane
afforded a yellow–orange powder, which was filtered and dried
in vacuo to give 5a (0.43 g, 80%). Spectroscopic data for 5a: 1H
NMR (CDCl3): δ 7.68–6.84 (m, 35H, Ph); 4.40 (dd, 1H, CH,
JH–H = 8.9, 7.8 Hz); 4.37 (s, 5H, Cp); 3.16, 2.86 (dd, 2H, CH2,
JH–H = 8.9, 7.8 Hz, JH–H = 13.9 Hz). 31P NMR (CDCl3): δ 42.2,
41.5 (AB, JP–P = 35.2 Hz). 13C NMR (CDCl3): δ 135.8–127.1
(Ph), 118.6 (CN); 83.7 (Cp); 40.8 (CH); 39.7 (CH2). MS (FAB):
m/z 897.9 (Mϩ Ϫ PF6), 691 (Mϩ Ϫ PF6, NCCHPhCH2Ph),
1
troscopic data for 10: H NMR (CDCl3): δ 7.76–6.85 (m, 5H,
Ph); 4.42 (dd, JH–H = 8.7, 6.4 Hz, 1H, CH); 3.72 (s, 3H, CH3);
3.44, 3.24 (dd, JH–H = 16.6, 8.7, 6.4 Hz, 2H, CH2). High reso-
lution MS: calc. for C11H11N5: m/z 213.1014, found: 213.1009.
᎐
Reaction of [Ru]–C᎐CPh with Me3SiN3
᎐
᎐
To a solution of complex [Ru]–C᎐CPh (0.11 g, 0.14 mmol) in
᎐
THF (20 ml) was added Me3SiN3 (0.10 mL, 0.75 mmol). After
J. Chem. Soc., Dalton Trans., 2001, 3154–3159
3157