Synthesis of [TpRu(CO)(PPh3)]2(μ-CH=CH-CH=CH-C6 H4-CH=CH-CH=CH) from Wittig reactions

Article abstract of DOI:10.1016/S0022-328X(03)00704-6

Treatment of [Ru(CH=CHCH₂PPh₃)X(CO) (PPh₃)₂]⁺ (X=Cl, Br) with KTp (Tp=hydridotris(pyrazolyl)borate) and NaBPh₄ produced [TpRu(CH=CHCH₂PPh₃)(CO)(PPh₃)] BPh

Full text of DOI:10.1016/S0022-328X(03)00704-6

Journal of Organometallic Chemistry 683 (2003) 331ꢂ336
/
www.elsevier.com/locate/jorganchem
Synthesis of [TpRu(CO)(PPh3)]2(m-CHÄ
/
CHÃ
/
CHÄ
/
CHÃ
/
C6H4Ã
/
CHÄ
/
CHÃCHÄCH) from Wittig reactions
/
/
Sheng Hua Liu, Haiping Xia, Kam Lok Wan, Richard C.Y. Yeung, Quan Yuan Hu,
Guochen Jia *
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
Received 28 April 2003
Abstract
Treatment of [Ru(CHÄ
produced [TpRu(CHÄCHCH2PPh3)(CO)(PPh3)]BPh4. Reaction of RuHCl(CO)(PPh3)3 with HCÅ
CHCH(OEt)2)Cl(CO)(PPh3)2, which reacted with KTp to give TpRu(CHÄCHCHO)(CO)(PPh3). Treatment of [TpRu(CHÄ
CHCH2PPh3)(CO)(PPh3)]BPh4 with NaN(SiMe3)2 and benzaldehyde produced TpRu(CHÄCHCHÄCHPh)(CO)(PPh3). The later
complex was also produced when TpRu(CHÄCHCHO)(CO)(PPh3) was treated with PhCH2PPh3Cl/NaN(SiMe3)2. The bimetallic
/
CHCH2PPh3)X(CO)(PPh3)2]ꢀ (Xꢁ
/
Cl, Br) with KTp (Tpꢁ
/
hydridotris(pyrazolyl)borate) and NaBPh4
/
/
CCH(OEt)2 produced Ru(CHÄ
/
/
/
/
/
/
complex [TpRu(CO)(PPh3)]2(m-CHÄ
/
CHÃ
/
CHÄ
/
CHÃ
/
C6H4Ã
/
CHÄ
/
CHÃ
/
CHÄ
/
CH) was obtained from the reaction of [TpRu(CHÄ
/
CHCH2PPh3)(CO)(PPh3)]BPh4 with NaN(SiMe3)2 and terephthaldicarboxaldehyde.
# 2003 Elsevier B.V. All rights reserved.
Keywords: Ruthenium; Alkenyl; Wittig reactions; Bimetallic
1. Introduction
biscarbene
complexes
(e.g.
{[CpFe(dppe)]2(m-
C(OR)CH2CH2C(OR)}2ꢀ), the reaction of [CpFe-
(CO)2]ꢃ with 3,4-dichlorocyclobutene, and ligand sub-
stitution reactions of preformed bimetallic alkenyl
complexes. Wittig reactions have been proved to be
one of the most efficient methods to synthesize olefins
from phosphonium salts and aldehydes or ketones. The
reactions have also been used recently in the synthesis of
organometallic complexes. For example, reactions of
Bimetallic complexes with conjugated hydrocarbon
ligands bridging metal centers are attracting consider-
able interest for their structural and material properties
[1]. In the past few years, many bimetallic complexes
with M-alkynyl linkages have been synthesized [2]. In
contrast, relatively few bimetallic complexes with M-
alkenyl linkages are known. Reported bimetallic com-
[(h5-C9H7)Ru(CÅ
and appropriate aldehydes or ketones lead to (h5-
C9H7)Ru(CÅCCHÄCRR?)(PPh3)2 [14]. Thus, one might
expect that Wittig reactions could also be used for the
synthesis of bimetallic complexes with M-alkenyl lin-
kages starting from alkenyl phosphonio derivatives
/CCH2PPh3)(PPh3)2]PF6 with LiBu
plexes with M-alkenyl linkages include those with (CHÄ
CH)n bridges (nꢁ1 [3], 2 [4ꢂ6], 3 [7], 4 [8]), C2R2 [9],
PhCÄCHÃCHÄCPh [10], C(OR)ÄCHÃCHÄCH(OR)
[11], and CHÄCHÃArÃCHÄCH [12,13]. The relatively
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
little exploration on the latter complexes may be
attributed, in part, to the lack of simple methods to
synthesize such complexes. Previous common routes to
prepare such bimetallic complexes involve the reactions
of dialkynes with LnMH, deprotonation of dicationic
[LnMCHÄ
/
CHCH2PR3]ꢀ
or
alkenyl
aldehydes
LnMCHÄCHCHO. However, such a possibility has
/
not been explored previously. In this paper, we wish to
report the synthesis of a bimetallic alkenyl complex via
Wittig reactions using [TpRu(CHÄ
(CO)(PPh3)]ꢀ or TpRu(CHÄ
CHCHO)(CO)(PPh3) as
the starting materials.
/
CHCH2PPh3)-
/
* Corresponding author.
E-mail address: chjiag@ust.hk (G. Jia).
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00704-6

332
S.H. Liu et al. / Journal of Organometallic Chemistry 683 (2003) 331ꢂ336
/
2. Results and discussion
2.1. Synthesis of ruthenium vinyl complexes with
phosphonium or aldehyde functional groups
In principle, bimetallic complexes [LnM]2(m-CHÄ
/
CHCHÄ
/
CHÃ
/
RÃ
/
CHÄ
/
CHCHÄ
/
CH) could be prepared
from the Wittig reactions of [LnMCHÄCHCH2PR?]ꢀ
3
with OCHÃ
/
RÃ
/
CHO or the reactions of LnMCHÄ
/
CHCHO with R?PCH2ÃRÃCH2PR?: Reactions of
3
3
RuHCl(CO)(PPh3)3 (1) with HCÅ
give Ru(CHÄ
has been used to prepare bimetallic complexes such as
[RuCl(CO)(PPh3)2]2(m-CHÄCHÃArÃCHÄCH) [12] and
[RuCl(CO)(PPh3)2]2(m-(CHÄCH)n) (nꢁ2, 3, 4) [6,7].
Thus, we have tried to prepare complexes
[LnRuCHÄCHCH2PR?]ꢀ and LnRu(CHÄ
CHCHO)
starting from the reactions of RuHCl(CO)(PPh3)3 with
HCÅCCH(OEt)2 and HCÅCCH2PPh3Br.
/CR are known to
/
CHR)Cl(CO)(PPh3)2 [15,16]. The reaction
/
/
/
/
/
/
/
3
/
/
The reaction of RuHCl(CO)(PPh3)3 with HCÅ
CCH2PPh3Br has previously been reported by Hill and
coworkers [17]. Under mild conditions, the reaction
/
produced
a
mixture of [Ru(CHÄ
/
CHCH2PPh3)-
Cl(CO)(PPh3)2]ꢀ
and
[Ru(CHÄ
/
CHCH2PPh3)-
Br(CO)(PPh3)2]ꢀ; in refluxing ethanol, the reaction
produced
CHCH2PPh3)Br(CO)(PPh3)2]ꢀ. Using the reported pro-
cedure, the complexes [Ru(CHÄCHCH2PPh3)Cl-
(CO)(PPh3)2]X (2a) and [Ru(CHÄCHCH2PPh3)-
Br(CO)(PPh3)2]X (2b) (XꢁCl or Br) were obtained
from the one-pot reaction of RuHCl(CO)(PPh3)3 with
HCÅCCH2PPh3Br. Attempts have been made to use 2
as the starting material to carry out Wittig reactions.
However, complex 2 decomposed when treated with
bases such as NaOH, KO(t-Bu), and LiN(i-Pr)2. The
failure of performing Wittig reactions of 2 may be due to
the complication that bases also attacked the halide
ligand in complex 2.
the
bromide
complex
[Ru(CHÄ
/
/
Scheme 1.
/
/
RuHCl(CO)(PPh3)3 (1) in dichloromethane produced
the
insertion
product
Ru(CHÄ
/
/
CHCH(OEt)2)Cl(CO)(PPh3)2 (4). The compound has
been characterized by NMR and elemental analysis. The
31P{1H}-NMR spectrum showed a singlet at 29.8 ppm,
which is typical for RuCl((E)-CHÄ
/
CHR)(CO)(PPh3)2.
The H-NMR spectrum displayed the RuÃCH signal at
7.8 ppm, the b-CH signal at 5.1 ppm, and the d-CH
signal at 4.6 ppm. Monomeric complexes Ru(RCÄ
1
/
/
In order to avoid the side reactions, we have prepared
CHR?)Cl(CO)(PPh3)2 are known to adopt a distorted
trigonal bipyramidal geometry around ruthenium with
the two PPh3 ligands in the apical positions [15]. Thus, it
is reasonable to assume that complex 4 has a similar
geometry around ruthenium.
the Tp complex [TpRu(CHÄ
(PPh3)]BPh4 (3) by treating 2 with KTp and NaBPh4
(Scheme 1). Related complexes such as TpRu(CHÄ
/
CHCH2PPh3)(CO)-
/
CHPh)(CO)(PPh3) and TpRuPh(CO)(PPh3) have been
reported previously [18]. Complex 3 has been character-
ized by NMR spectroscopy and elemental analysis. In
particular, the 31P{1H}-NMR spectrum showed two
Complex 4 reacted with KTp to give TpRu(CHÄ
/
CHCHO)(CO)(PPh3) (5) which was isolated as a white
solid after purification by column chromatography.
Apparently, the CH(OEt)2 group has been hydrolyzed
to give the CHO group under the reaction conditions.
The 31P{1H}-NMR spectrum showed a singlet at 46.9
5
doublets at 15.8 and 48.6 ppm with J(PP) of 2.5 Hz.
1
1
The H-NMR spectrum showed the H signals of CHÄ
CHCH2 at 7.8 (RuÃCH), 4.8 (b-CH), and 3.6 (CH2)
ppm. The 13C-NMR spectrum showed the 13C signals of
CHÄCHCH2 at 175.4 (RuÃCH), 125.5 (b-CH), and 32.3
(CH2) ppm and that of CO at 206.0 ppm.
/
/
ppm. The 1H-NMR spectrum displayed the RuÃ
signal at 9.9 ppm, the b-CH signal at 6.5 ppm, and the d-
CHO signal at 9.1 ppm. The relatively down-field
/CH
/
/
The alkenyl aldehyde complex TpRu(CHÄ
CHCHO)(CO)(PPh3) (5) was prepared using similar
methodology (Scheme 1). Addition of commercially
/
chemical shift of the RuÃ
/
CH signal (9.9 ppm) may
indicate that both forms 5 and 5A have substantial
available HCÅ/CCH(OEt)2 to
a
suspension of
contribution to the structure.

S.H. Liu et al. / Journal of Organometallic Chemistry 683 (2003) 331ꢂ
/336
333
2.2. Wittig reactions of [TpRu(CHÄ
/
CHCH2PPh3)(CO)(PPh3)]BPh4 and TpRu(CHÄ
/
CHCCHO)(CO)(PPh3)
Scheme 2.
To test the feasibility of using Wittig reactions to
synthesize bimetallic complexes, the Wittig reactions
which is similar to that of 6. The presence of CHÄ
/
1
CHAr group in complex 7 is indicated by H-
using [TpRu(CHÄ
/
CHCH2PPh3)(CO)(PPh3)]BPh4 (3)
CHCHO)(CO)(PPh3) (5) as the starting
CHCHÄ
/
1
NMR spectroscopy. In particular, the H-NMR spec-
and TpRu(CHÄ
/
1
materials have been carried out.
Treatment of 3 with NaN(SiMe3)2 produced a red
solution, which readily reacted with benzaldehyde to
trum showed the H signals of CHÄ
7.82 (RuÃCH), 6.32 (b-CH), 6.70 (g-CH), and 5.91 (d-
CH) ppm. Reported complexes related to 7 include
bisalkenyl complexes LnMÃCHÄCHÃArÃCHÄCHÃ
MLn [12,13] and biscarbene complexes LnMÄC(OR)Ã
CHÄCHÃArÃCHÄCHÃC(OR)ÄMLn [19].
/
CHCHÄ
/
CHAr at
/
give TpRu(CHÄ
Wittig reaction appeared to be complete within 30 min
and two isomers of (EE)- and (EZ)-TpRu(CHÄ
CHCHÄCHPh)(CO)(PPh3) were produced in a ratio
of ca. 2:1. The presence of CHÄCHCHÄCHPh in
complex 6 is clearly indicated by the H-NMR spectro-
scopy. In the 1H-NMR spectrum, the 1H signals of CHÄ
CHCHÄCHPh of 6a were observed at 7.9 (RuÃCH), 6.4
(b-CH), 6.8 (g-CH), and 6.0 (d-CH) ppm, and those of
6b were observed at 8.1 (RuÃCH), 6.9 (b-CH), 6.2 (g-
CH), and 5.7 (d-CH) ppm. Complex 6 was also
produced when the complex
TpRu(CHÄ
CHCHO)(CO)(PPh3) was treated with the ylide
PhCHÄPPh3 (generated from the reaction of
/
CHCHÄ/CHPh)(CO)(PPh3) (6). The
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
1
/
3. Summary and conclusion
/
/
The functionalized ruthenium complexes [TpRu(CHÄ
/
/
CHCH2PPh3)(CO)(PPh3)]BPh4 and
CHCHO)(CO)(PPh3) have been prepared. These
TpRu(CHÄ
/
/
complexes can be used as starting materials for
Wittig
[TpRu(CO)(PPh3)]2(m-CHÄ
CHÃCHÄCH) was obtained from the reaction
of [TpRu(CHÄCHCH2PPh3)(CO)(PPh3)]BPh4 with
reactions.
The
bimetallic
complex
/
/
CHÃ
/
CHÄCHÃ
/
/
C6H4ÃCHÄ
/
/
PhCH2PPh3Cl with NaN(SiMe3)2). However, the reac-
tion is slow. For example, only a small amount of the
expected product was formed, after the reaction mixture
was allowed to stand for 12 h at room temperature. The
reaction proceeded slowly when the reaction mixture is
heated at 50 8C. Under the reaction condition, the
reaction is completed in 48 h to give two isomers of
/
/
/
NaN(SiMe3)2 and terephthaldicarboxaldehyde.
(EE)- and (EZ)-TpRu(CO)(PPh3)(CHÄ
/
CHÃ
/
CHÄ
/
CHÃ
/
4. Experimental
Ph) in a ratio of ca. 2:1.
All manipulations were carried out at room tempera-
ture (r.t.) under a nitrogen atmosphere using standard
Schlenk techniques, unless otherwise stated. Solvents
were distilled under nitrogen from sodium benzophe-
none (hexane, diethyl ether, THF, benzene) or calcium
hydride (dichloromethane, CHCl3). The starting materi-
als KTp [20] and RuHCl(CO)(PPh3)3 [21] were prepared
according to literature methods. Microanalyses were
performed by M-H-W Laboratories (Phoenix, AZ). 1H-,
13C{1H}-, and 31P{1H}-NMR spectra were collected on
2.3. Synthesis of bimetallic complexes
We have tried to prepare bimetallic complexes from 3.
In THF, the ylide TpRu(CHÄCHCHÄPPh3)(CO)(PPh3)
(generated from reaction of [TpRu(CHÄCHÃ
/
/
/
/
CH2PPh3)(CO)(PPh3)]BPh4 with NaN(SiMe3)2) reacted
with terephthaldicarboxaldehyde to give a mixture of
species, from which pure complex 7 can be isolated after
purification by chromatography (Scheme 2). Complex 7
has been characterized by NMR spectroscopy and
elemental analysis. The 31P{1H}-NMR spectrum
showed a singlet at 48.8 ppm, the chemical shift of
1
a Bruker ARX-300 spectrometer (300 MHz). H- and
13C-NMR chemical shifts are relative to TMS, and 31P-
NMR chemical shifts are relative to 85% H3PO4.

334
S.H. Liu et al. / Journal of Organometallic Chemistry 683 (2003) 331ꢂ336
/
1
4.1. [Ru(CHÄ
and [Ru(CHÄ
(XꢁCl or Br)
/
CHCH2PPh3)Cl(CO)(PPh3)2]X (2a)
CDCl3): d 32.3 (d, J(PC)ꢁ
RuÃCHÄ
CH), 175.4 (t, 2J(PC)ꢁ
206.0 (d, J(PC)ꢁ
Tp, PPh3, BPh4). IR (KBr, cmꢃ1): yCO
/
45.1 Hz, CH2), 125.5 (m,
12.7 Hz, RuÃCH),
CO), 105.2ꢂ164.9 (m,
1936 s.
/
CHCH2PPh3)Br(CO)(PPh3)2]X (2b)
/
/
/
/
2
/
/
16.0 Hz, RuÃ
/
/
ꢁ
/
To a suspension of RuHCl(CO)(PPh3)3 (1) (2.5 g, 2.6
mmol) in dichloromethane (20 ml) was added HCÅ
/
CCH2PPh3Br (1.05 g, 2.75 mmol). The reaction mixture
was stirred at r.t. for 20 min to give a yellow suspension.
The volume of the reaction mixture was then reduced to
ca. 5 ml under vacuum. Addition of ether (50 ml) to the
reaction mixture produced a yellow solid, which was
4.3. Ru(CHÄ
/
CHCH(OEt)2)Cl(CO)(PPh3)2 (4)
HCÅCCH(OEt)2 (0.30 ml, 1.8 mmol) was slowly
/
added to a suspension of RuHCl(CO)(PPh3)3 (1) (1.00
g, 1.05 mmol) in dichloromethane (20 ml). The mixture
was stirred at r.t. for 5 min to give a red solution. The
volume of the reaction mixture was reduced to ca. 5 ml
under vacuum. n-Hexane (30 ml) was added to the
reaction mixture to give a yellow solid, which was
collected by filtration, washed with chloroform (2ꢄ
ml) and diethyl ether (3ꢄ30 ml), and dried under
vacuum. Yield: 2.8 g, 98%. The NMR spectra of the
solid show that it is
mixture of [Ru(CHÄ
CHCH2PPh3)Cl(CO)(PPh3)2]X (2a, major) and
[Ru(CHÄCHCH2PPh3)Br(CO)(PPh3)2]X (2b, minor)
(Xꢁ
Cl or Br) in a ratio of ca. 3:1. 31P{1H}-NMR
/
5
/
a
/
collected by filtration, washed with n-hexane (3ꢄ30
/
/
ml), and dried under vacuum. Yield: 0.50 g, 58%. Anal.
Calc. for C44H43ClO3P2Ru: C, 64.54; H, 5.3. Found: C,
/
(121.50 MHz, CD2Cl2): d 16.7 (s, CH2PPh3), 25.3 (s,
RuPPh3) (major); 16.9 (s, CH2PPh3), 26.3 (s, RuPPh3)
(minor). The compounds have been previously reported
by Hill and coworkers [17].
1
64.6; H, 5.16%. H-NMR (300.13 MHz, CDCl3): d 1.1
(t, 3J(HH)ꢁ
7.0 Hz, 6H, OCH2CH3), 3.1 (dq,
/
2J(HH)ꢁ
/
9.3 Hz, J(HH)ꢁ
/
7.0 Hz, 2H, OCHHCH3),
7.0 Hz, 2H,
3
3.3 (dq, 2J(HH)ꢁ
/
9.3 Hz, 3J(HH)ꢁ
/
3
OCHHCH3), 4.6 (d, J(HH)ꢁ
(ddt, 3J(HH)ꢁ
CHÄCH), 7.4ꢂ
/
6.5 Hz, 1H, g-CH), 5.1
/
4.2. [TpRu(CHÄ
/
CHCH2PPh3)(CO)(PPh3)]BPh4
/
13.2, 6.5 Hz, 4J(PH)ꢁ
/
2.0 Hz, 1H, RuÃ
(3)
3
/
/
7.7 (m, 30H, PPh3), 7.8 (d, J(HH)ꢁ
/
13.2 Hz, 1H, RuÃ
/
CH). 31P{1H}-NMR (121.50 MHz,
A mixture of 2 (1.72 g, 1.61 mmol) and KTp (0.65 g,
2.58 mmol) in dichloromethane (60 ml) was stirred for 1
h to give a red solution and a white precipitate. The
volume of the reaction mixture was reduced to ca. 40 ml
under vacuum. Diethyl ether (30 ml) was then added.
The resulting mixture was stirred for 30 min and then
filtered through a column of Celite to remove the KCl
and KBr salts. The volume of the filtrate was reduced to
ca. 5 ml under vacuum. Addition of diethyl ether (60 ml)
to the residue produced a pale orange solid, which
was collected by filtration, washed by ether
CDCl3): d 29.8 (s, PPh3). 13C{1H}-NMR (75.47 MHz,
CDCl3): d 15.1 (OCH2CH3), 60.4 (s, OCH2CH3), 103.1
(s, CH(OEt)2), 127.6ꢂ
146.4 (t, 2J(PC)ꢁ
11.2 Hz, RuÃ
14.9 Hz, RuÃ
CO). IR (KBr, cmꢃ1): yCO
/
134.4 (m, RuÃ
CH), 201.2 (t, 2J(PC)ꢁ
1940 s.
/
CHÄ
/
CH, PPh3),
/
/
/
/
ꢁ
/
4.4. TpRu(CHÄ
/
CHCHO)Cl(CO)(PPh3)2 (5)
A mixture of complex 4 (1.00 g, 1.22 mmol) and KTp
(0.36 g, 1.43 mmol) in dichloromethane (30 ml) was
stirred for 2 h. Then diethyl ether (30 ml) was added and
the reaction mixture was stirred for additional 30 min.
The reaction mixture was then filtered through a column
of Celite to obtain a greenish filtrate. The filtrate was
passed through a silica gel column under a N2 atmo-
sphere with the following eluents: n-hexane (80 ml),
dichloromethane (100 ml), and methanol (80 ml). The
methanol eluent was collected and concentrated to
obtain a white solid, which was collected and dried
under vacuum. Yield: 0.25 g, 32%. Anal. Calc. for
C31H28BN6O2PRu: C, 56.35; H, 4.28; N, 12.73. Found:
(2ꢄ
(yield: 81%) of
CHCH2PPh3)(CO)(PPh3)]X (Xꢁ
CHCH2PPh3)(CO)(PPh3)]BPh4 was obtained from
[TpRu(CHÄCHCH2PPh3)(CO)(PPh3)]X (XꢁCl, Br)
as follows: mixture of
[TpRu(CHÄ
CHCH2PPh3)(CO)(PPh3)]X (XꢁCl, Br) (1.85 g, 1.88
/
30 ml), and dried under vacuum to give 1.29 g
white solid of [TpRu(CHÄ
Br, Cl). [TpRu(CHÄ
a
/
/
/
/
/
a
/
/
mmol) and NaBPh4 (1.6 g, 4.7 mmol) in methanol (40
ml) was stirred for 15 min to give a white solid, which
was collected by filtration, washed by methanolꢂwater
/
(1:1 mixture) followed with methanol and diethyl ether,
and dried under vacuum. Yield: 1.77 g, 89.6%. Anal.
Calc. for C73H64B2N6OP2Ru: C, 71.43; H, 5.26; N, 6.85.
1
C, 56.36; H, 4.43; N, 12.86%. H-NMR (300.13 MHz,
1
Found: C, 71.38; H, 5.40; N, 6.66%. H-NMR (300.13
CD2Cl2): d 6.5 (dd, 3J(HH)ꢁ
/
16.4 Hz, 8.0 Hz, 1H, RuÃ
7.7 (m, 25H, PPh3, Tp), 9.1 (d,
8.0 Hz, 1H, CHO), 9.9 (d, 3J(HH)ꢁ
16.4
Hz, 1H, RuÃ
CH). 31P{1H}-NMR (121.50 MHz, ace-
tone-d6): d 46.9 (s, PPh3). IR (KBr, cmꢃ1): yCO
1944.9
s, yCHO 1650 s.
/
MHz, acetone-d6): d 3.6 (m, 2H, CH2), 4.8 (m, 1H, RuÃ
CHÄCH), 5.7ꢂ7.7 (m, 60H, Tp, PPh3, BPh4), 7.8 (m,
1H, RuÃ
CH). 31P{1H}-NMR (121.50 MHz, acetone-
d6): d 15.8 (d, 5J(PP)ꢁ
2.5 Hz, CH2PPh3), 48.6 (d,
5J(PP)ꢁ2.5 Hz, RuPPh3). 13C{1H}-NMR (75.47 MHz,
/
CHÄ
/
CH), 5.9ꢂ
/
/
/
3J(HH)ꢁ
/
/
/
/
/
ꢁ
/
/
ꢁ
/

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/336
335
4.5. TpRu(CHÄ
/
CHCHÄ
/
CHPh)(CO)(PPh3) (6)
4.6. [TpRu(CO)(PPh3)]2(m-CHÄ
/
CHÃ
/
CHÄ
/
CHÃ
/
C6H4ÃCHÄCHÃCHÄCH) (7)
/
/
/
/
4.5.1. Method A
A THF solution of NaN(SiMe3)2 (1 M, 1 ml, 1 mmol)
was added dropwise to a Schlenk flask containing
To
a
solution
of
[TpRu(CHÄ
/
CHÃ
/
CH2PPh3)(CO)(PPh3)]BPh4 (1.00 g, 0.82 mmol) in
THF (30 ml) was added NaN(SiMe3)2 (0.5 ml, 1
mmol, 2 M in THF). The reaction mixture was stirred
for 30 min to give a red solution. Then, terephthaldi-
carboxaldehyde (0.054 g, 0.40 mmol) in THF (20 ml)
was slowly added to the reaction mixture over a period
of 2 h. The reaction mixture was stirred for additional 2
h and then quenched with water (0.3 ml). The solvents
were then removed completely. The 31P-NMR spectrum
of the residue showed two peaks at 48.8 and 49.1 ppm in
about 9:2 ratio, indicating the formation of isomers. The
major isomer was obtained in pure form by column
chromatography (silica gel, eluent: CH2Cl2) and was
identified to be the (EE)-isomer. Anal. Calc. for
C70H62B2N12O2P2Ru2: C, 60.53; H, 4.50; N, 12.10.
Found: C, 60.35; H, 4.70; N, 11.94%. 1H-NMR
(300.13 MHz, CDCl3): d 5.91 (d, 2H, J(HH)ꢁ
Hz, d-CH), 6.32 (dd, J(HH)ꢁ
CH), 6.70 (dd, 3J(HH)ꢁ
5.85ꢂ
Hz, 3J(PH)ꢁ
complex [TpRuÃ
/
CHÄ/CHCH2PPh3)(CO)(PPh3)]BPh4
(0.60 g, 0.49 mmol) and THF (30 ml). The reaction
mixture was stirred for 10 min and then benzaldehyde
(200 l, 1.96 mmol) was added to give a yellow solution
with a white precipitate. After the reaction mixture was
stirred for 20 min, it was filtered through a column of
Celite. The solvent of the filtrate was completely
removed under vacuum to give a yellow solid. The solid
was redissolved in ca. 3 ml of benzene and n-hexane (60
ml) was added to generate an orange precipitate. The
solid was separated by filtration and the yellow filtrate
was collected. The solvent of the yellow filtrate was
completely removed under vacuum to give a yellow
solid, which was washed with hexane and dried under
vacuum. Yield: 0.17 g, 47%. 1H- and 31P{1H}-NMR
spectra show that both (EE)- and (EZ)-isomers of
3
/15.0
3
/
15.9, 10.2 Hz, 2H, b-
TpRu(CHÄ
/
CHCHÄ
/
CHPh)(CO)(PPh3) are present
2:1). Anal. Calc. for
C38H34BN6OPRu: C, 62.11; H, 4.67; N, 11.44. Found:
/
15.0, 10.2 Hz, 2H, g-CH),
3
/
((EE)-isomer:(EZ)-isomerꢁ
/
/
7.64 (m, 54H, Tp, Ph), 7.82 (dd, J(HH)ꢁ
15.9
/
1.8 Hz, 2H, RuÃ
/
CH). 31P{1H}-NMR
C, 61.81; H, 4.90; N, 11.27%. IR (KBr, cmꢃ1): yCO
ꢁ
/
(121.50 MHz, CDCl3): d 48.8 (s).
1936 s.
Acknowledgements
4.5.2. Method B
To an NMR tube charged with PhCH2PPh3Cl (39
mg, 0.10 mmol) and THF (0.5 ml) was added
NaN(SiMe3)2 (0.05 ml, 2 M in THF, 0.1 mmol). After
the mixture was stood for 30 min, a solution of
The authors acknowledge financial support from the
Hong Kong Research Grants Council.
TpRu(CHÄ/CHCHO)(CO)(PPh3) (33 mg, 0.05 mmol)
References
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