Hydrolysis of osmium and ruthenium carbyne complexes

Article abstract of DOI:10.1021/om200685v

Hydrolysis reactions of MCl₃(≡CCH=C(ArCl) ₂)(PPh₃)₂ (M = Ru, Os) were investigated. Treatment of OsCl₃(≡CCH=C(o,o′-C₆H ₃Cl₂)₂)(PPh₃)₂ with water produced the six-membered metallacycle OsCl(κC,κCl-CH=C(o,o′- C₆H₃Cl₂)₂)(CO)(PPh₃) ₂. Reactions of MCl₃(≡CCH=C(o-C₆H ₄Cl)₂)(PPh₃)₂ (M = Ru, Os) produced the related six-membered metallacycles MCl(κC,κCl-CH=C(o-C ₆H₄Cl)₂)(CO)(PPh₃)₂.

Full text of DOI:10.1021/om200685v

Article
pubs.acs.org/Organometallics
Hydrolysis of Osmium and Ruthenium Carbyne Complexes
Jiangxi Chen, Herman Ho-Yung Sung, Ian Duncan Williams, and Guochen Jia*
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
S
* Supporting Information
ABSTRACT: Hydrolysis reactions of MCl3(CCHC(ArCl)2)(PPh3)2
(M = Ru, Os) were investigated. Treatment of OsCl3(CCHC(o,o′-
C6H3Cl2)2)(PPh3)2 with water produced the six-membered metallacycle
OsCl(κC,κCl-CHC(o,o′-C6H3Cl2)2)(CO)(PPh3)2. Reactions of MCl3
(CCHC(o-C6H4Cl)2)(PPh3)2 (M = Ru, Os) produced the related six-
membered metallacycles MCl(κC,κCl-CHC(o-C6H4Cl)2)(CO)(PPh3)2.
During the process, we found that 3 can react with H2O to
give an interesting six-membered metallacycle involving a
bridging chloride of the aryl ring.
Complex 3 was prepared from the one-pot reaction of
OsCl2(PPh3)3 (1) with alkynol 2 and HPPh3BF4 in the
presence of NaCl in CH2Cl2 (Scheme 1). Its structure has been
confirmed by X-ray diffraction. The molecular structure of 3 is
shown in Figure 1, and selected bond distances and angles are
given in Table 1. The solid-state structure is supported by
solution NMR data.
INTRODUCTION
■
There has been much interest in the chemistry of carbyne
complexes of group 8 metals, especially those of ruthenium and
osmium,1 because of their relevance to catalysis and/or
synthesis of organometallic and organic compounds. Ruthe-
nium and osmium alkenylcarbyne complexes represent a
particularly interesting class of carbyne complexes of group 8
metals. In the past, a number of alkenylcarbyne complexes of
ruthenium2,3 and osmium4,5 have been reported. Interesting
reactions of such complexes have also been revealed. For
example, complexes such as [(p-cymene)RuCCHCAr2)-
(PR3)]2+,6 RuCl3(CCHCPh2)(PPh3)2,7 and [CpOs-
(CCHCPh2)(PiPr3)(CO)](PF6)28 can rearrange to indenyli-
dene complexes. The osmium complex [Os(CHCHPh)(
CCHCPh2)(CH3CN)2(PiPr3)2][BF4]2 reacts with carbon
monoxide to give a dienylcarbene derivative.9 Osmium
complexes of the type [OsLn(R′)(CCHCR2)]n+ (R′ = H,
vinyl) react with neutral ligands L′ such as CH3CN to give the
carbene complexes [OsLnL′(CR′CHCR2)]n+.10 Ruthenium
complexes of the type [Cp*Ru(CCHCRR′)(dippe)]-
[BF4]2 (dippe = 1,2-bis(diisopropylphosphino)ethane) react
with a variety of reagents such as ketones, 1,3-dicarbonyl
compounds, and aromatic compounds at the γ-carbon to give a
series of alkylated vinylidene complexes.11 Osmium complexes
such as OsCl3(CCHCRCHCR′Cl)(PPh3)2 and
OsCl3(CCHC(o-C6H4Cl)2)(PPh3)2 can be used to
prepare osmabenzyne complexes through their zinc reduction
reactions.12 In this work, we report hydrolysis reactions of
MCl3(CCHC(o-ArCl)2)(PPh3)2 (M = Ru, Os), which
lead to the isolation of six-membered metallacycles involving a
bridging chloride of the aryl ring.
Complex 3 can be stored as a solid under an inert
atmosphere for months without appreciable decomposition.
As monitored by NMR, complex 3 was slowly converted to a
new species in a wet THF solution. Further investigation shows
that the new species is the interesting six-membered metalla-
cycle OsCl(κC,κCl-CHC(o,o′-C6H3Cl2)2)(CO)(PPh3)2 (4)
(Scheme 1). The conversion was almost complete after a
mixture of 3 and excess (ca. 49 equiv of) H2O suspended in
THF was stirred at room temperature for 12 h or heated at
50 °C for 8 h (Scheme 1).
Complex 4 was isolated as a yellow solid and has been
characterized by NMR and elemental analysis as well as X-ray
diffraction. The molecular structure of 4 is shown in Figure 2,
and selected bond distances and angles are given in Table 2. As
shown in Figure 2, the complex can be described as a distorted
octahedron containing two trans PPh3 ligands and two cis
chloride ligands. The most interesting feature of the structure is
that it contains a nonplanar six-membered metallacycle with
one of the chlorides of the aryl rings bound to osmium. The
Os−C1 bond distance of 2.045(2) Å is within the range of Os−
C(vinyl) bonds (1.897−2.195 Å).13,14 The Os−Cl2(bridged)
bond (2.5385(6) Å) is longer than the Os−Cl1(terminal) bond
(2.4811(6) Å) and is close to that (2.574(1) Å) in the related
complex OsH(κO,κCl-OC6Cl5)(CO)(PiPr3)2.15 The C(4)−
Cl(2)−Os(1) angle (106.77(8)°) is significantly larger than
that in OsH(κO,κCl-OC6Cl5)(CO)(PiPr3)2 (98.4(2)°).15
RESULTS AND DISCUSSION
■
Hydrolysis Reaction of mer-OsCl3(CCHC(o,o′-
C6H3Cl2)2)(PPh3)2. We have recently shown that the osmium
complex OsCl3(CCHC(o-C6H4Cl)2)(PPh3)2 can react
with zinc to give an osmanaphthalyne complex.12a In an effort
to extend the chemistry, we have prepared the related carbyne
complex OsCl3(CCHC(o,o′-C6H3Cl2)2)(PPh3)2 (3).
Received: July 26, 2011
Published: November 3, 2011
© 2011 American Chemical Society
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Scheme 1
Figure 1. ORTEP drawing of 3 with ellipsoids at the 35% probability
level. The hydrogen atoms on the PPh3 ligands are omitted for clarity.
Figure 2. ORTEP drawing of 4 with ellipsoids at the 50% probability
level. The solvent and the hydrogen atoms on the PPh3 ligands are
omitted for clarity.
Table 1. Selected Bond Distances (Å) and Angles (deg) for
Osmium Carbyne Complexes OsCl3(CCHC(o,o′-
C6 H3 Cl2 )2 )(PPh3 )2 (3) and OsCl3 (CCHC-
(o-C6H4Cl)2)(PPh3)2 (5)
Table 2. Selected Bond Distances (Å) and Angles (deg) for
M e t a l l a c y c l e s O s C l ( κ C , κ C l - C H  C ( o , o ′ -
C6H3Cl2)2)(CO)(PPh3)2 (4) and RuCl(κC,κCl-CHC-
(o-C6H4Cl)2)(CO)(PPh3)2 (10)
3
5
Os(1)−P(1)
Os(1)−P(2)
Os(1)−Cl(1)
Os(1)−Cl(2)
Os(1)−Cl(3)
Os(1)−C(1)
C(1)−C(2)
C(2)−C(3)
C(2)−C(1)−Os(1)
C(1)−Os(1)−P(1)
C(1)−Os(1)−P(2)
C(1)−Os(1)−Cl(1)
C(1)−Os(1)−Cl(2)
C(1)−Os(1)−Cl(3)
2.4427(14)
2.4797(14)
2.3687(12)
2.4516(13)
2.4062(12)
1.755(5)
2.431(2)
2.4416(19)
2.3756(16)
2.4607(16)
2.4252(16)
1.744(6)
1.416(8)
1.347(8)
166.4(5)
94.6(2)
4 (M = Os)
10 (M = Ru)
M(1)−C(1)
C(1)−C(2)
C(2)−C(3)
C(3)−C(4)
C(4)−Cl(2)
M(1)−Cl(2)
M(1)−Cl(1)
M(1)−C(20)
2.045(2)
1.355(3)
1.483(3)
1.405(3)
1.754(2)
2.5385(6)
2.4811(6)
1.813(2)
2.3905(6)
2.3842(6)
133.77(18)
124.4(2)
123.9(2)
118.48(18)
106.77(8)
81.58(7)
83.116(19)
168.52(7)
86.95(10)
163.26(6)
86.86(6)
102.48(6)
2.057(5)
1.369(9)
1.485(9)
1.383(9)
1.755(6)
2.5150(16)
2.4853(15)
1.824(7)
2.4137(15)
2.3774(15)
133.0(5)
126.1(6)
126.1(6)
121.0(5)
109.6(2)
84.28(18)
85.91(5)
172.53(19)
88.4(3)
1.408(7)
1.347(7)
170.1(4)
92.72(16)
93.23(16)
96.58(16)
176.77(15)
91.31(16)
M(1)−P(1)
M(1)−P(2)
91.9(2)
96.7(2)
M(1)−C(1)−C(2)
C(1)−C(2)−C(3)
C(2)−C(3)−C(4)
C(3)−C(4)−Cl(2)
C(4)−Cl(2)−M(1)
Cl(2)−M(1)−C(1)
Cl(2)−M(1)−Cl(1)
Cl(2)−M(1)−C(20)
C(1)−M(1)−C(20)
C(1)−M(1)−Cl(1)
C(1)−M(1)−P(1)
C(1)−M(1)−P(2)
175.6(2)
87.3(2)
Consistent with the solid-state structure, the 13C{1H} NMR
spectrum of 4 shows the Os−CH signal as a triplet at 158.1 ppm
with a JPC coupling constant of 5.5 Hz, the Os−CHC signal
as a singlet at 141.6 ppm, and the CO signal at 180.0 ppm
as a triplet with a JPC coupling constant of 11.7 Hz. As
indicated by the solid-state structure shown in Figure 2, the six-
membered metallacycle of 4 is not planar and therefore the two
PPh3 ligands are magnetically inequivalent. At room temper-
ature, the 31P{1H} NMR spectrum of 4 shows a sharp singlet at
7.5 ppm, indicating that the conformation of the six-membered
metallacycle changes rapidly in solution at this temperature.
169.46(17)
88.72(16)
94.07(16)
The fluxional process is slowed down at low temperature. Thus,
two doublet 31P{1H} signals were observed when the
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temperature was below −41 °C. For example, the 31P{1H}
NMR spectrum at −78 °C shows two doublets at 9.64 and 5.89
ppm with a large JPP coupling constant of 275.8 Hz, as expected
for two trans-disposed PPh3 ligands.
Scheme 2 shows a plausible mechanism for the formation of
4 from the reaction of 3 with H2O. Water could serve as a
studied the reaction of mer-OsCl3(CCHC(o-C6H4Cl)2)-
(PPh3)2 (5) with H2O under similar reaction conditions.
It was found that mer-OsCl3(CCHC(o-C6H4Cl)2)-
(PPh3)2 (5) is less reactive toward H2O than complex 3.
When a mixture of 5 and excess (ca. 270 equiv of) H2O
suspended in THF was stirred at 50 °C for 22 h, complex 5 was
partially converted to the expected product 6, which was
isolated in about 26% yield (Scheme 1).
Scheme 2
The identity of the complex 6 is inferred from its 31P and 13
C
NMR data. The 31P{1H} NMR spectrum shows two doublets at
9.37 and 4.41 ppm with a large JPP coupling constant of 286.2
Hz, as expected for two trans-disposed PPh3 ligands. In the
13C{1H} NMR spectrum, the CO signal was observed at 179.9
ppm as a triplet with a JPC coupling constant of 11.6 Hz. The
signal of Os−CH was located at 150.5 ppm as a triplet with a
JPC coupling constant of 6.2 Hz, and that of Os−CHC was
located at 145.7 ppm as a singlet.
We also studied the reaction of mer-OsCl3(CCH
CPh2)(PPh3)2 with H2O. No appreciable reaction was observed
after a suspension of mer-OsCl3(CCHCPh2)(PPh3)2 and
excess H2O in THF was stirred at room temperature for 1 week
or heated at 50 °C for 1 day.
Hydrolysis Reactions of mer-RuCl3(CCHC-
(o-C6H4Cl)2)(PPh3)2 (9). We next studied the reaction of the
related ruthenium carbyne complex mer-RuCl3(CCHC-
(o-C6H4Cl)2)(PPh3)2 (9) with H2O. Complex 9 can be prepared
from the one-pot reaction of RuCl2(PPh3)3 (7) with alkynol 8
and HCl in CH2Cl2 (Scheme 1). Its structure is inferred by its
solution NMR data. In particular, the 31P{1H} NMR spectrum
1
of 9 shows a singlet at 13.7 ppm and the H NMR spectrum
shows the RuCCH signal at 5.29 ppm as a triplet with a JPH
coupling constant of 2.2 Hz. The NMR data are similar to those
of the analogous complex mer-RuCl3(CCHCPh2)-
(PPh3)2.7
It was found that complex 9 is more reactive toward H2O
than complex 5. When a mixture of 9 and excess (ca. 73 equiv
of) H2O was stirred at room temperature for 40 min, it was
completely transformed to complex 10 (Scheme 1).
Complex 10 has been characterized by NMR and elemental
analysis as well as X-ray diffraction. The molecular structure of
10 is shown in Figure 3, and selected bond distances and angles
are given in Table 2. Overall, the structure is similar to that of 4.
nucleophile to attack the carbyne carbon of 3 to give
intermediate A, which can eliminate a molecule of HCl to
give B. A β-H elimination of B would give C, which undergoes
CO deinsertion and elimination of another molecule of HCl to
give D. The final product 4 could then be formed by
coordinating one of the chlorides of the aryl groups to the
osmium center.
Reactions of Fischer carbynes with nucleophiles at the
carbyne carbon to give carbene complexes are well-known
reactions.16 For osmium carbyne complexes, nucleophilic
addition reactions of methanol have been reported: for
example, the reactions of CpOs(CPh)(L) (L = PiPr3,
PiPr2CHCH2) with MeOH to give CpOsH(C(OMe)Ph)-
(L)17 and the reaction of [Os(CPh)(NH3)5]3+ with MeOH to
give [Os(C(OMe)Ph)(NH3)5]2+.18
Complex 4 is interesting because it represents a rare example
of six-membered haloarene complexes of osmium. A search of
the CCDC database shows that [OsCl(κO,κCl-OC6Cl5)(CO)-
15
(PiPr3)2 is the only reported structurally characterized
haloarene complex of osmium, although a number of haloraene
complexes of other transition metals are known.19 Furthermore,
most of the reported chelating chloroarene complexes are
either five-membered-ring20 or four-membered-ring21 metalla-
cycles. Complex 4 appeared to be the first structurally
characterized six-membered chelating chloroarene transition-
metal complex.
Hydrolysis Reaction of mer-OsCl3(CCHC-
(o-C6H4Cl)2)(PPh3)2. In order to see whether a similar reaction
can also occur for other osmium carbyne complexes, we have
Figure 3. ORTEP drawing of 10 with ellipsoids at the 35% probability
level. The solvent and the hydrogen atoms on PPh3 ligands are
omitted for clarity.
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128.4 (s, PhCl2), 126.8 (t, J(PC) = 5.0 Hz, PPh). Anal. Calcd for
C51H37Cl7OsP2: C, 53.26; H, 3.24. Found: C, 53.34; H, 3.40.
The Ru−C1 bond distance of 2.057(5) Å is within the range of
Ru−C(vinyl) bonds (1.973−2.161 Å).13,22 As expected, the
Ru−Cl2(bridged) bond (2.5150(16) Å) is longer than the Ru−
Cl1(terminal) bond (2.4853(15) Å). The Ru−Cl2(bridged)
bond (2.5150(16) Å) is close to those (2.5240(13), 2.4978(13)
OsCl(κC,κCl-CHC(o,o′-C6H3Cl2)2)(CO)(PPh3)2 (4). To a sus-
pension of 3 (260 mg, 0.226 mmol) in THF (20 mL) was added H2O
(0.2 mL, 11.1 mmol). The mixture was stirred at 50 °C for 8 h to give
a clear yellow solution. The solvent was removed completely under
vacuum, and the residue was loaded on a silica gel column that was
flashed with dichloromethane/hexane (v/v 1/4) and then eluted with
dichloromethane/hexane (v/v 10/1). The yellow band was collected.
The solvents were removed under vacuum to give 4 as a yellow solid.
Yield: 174 mg, 70.4%. 31P{1H} NMR (161.98 MHz, CD2Cl2, 25 °C): δ
7.5 (s). 31P{1H} NMR (161.98 MHz, CD2Cl2, −78 °C): δ 9.64 (d,
23
Å) in Ru(PPh2CH2CH2PiPr2)(κO,κCl-OC6Cl5)2 and shorter
than those (2.547(2), 2.604(2) Å) in Ru3(CO)8(κO,κCl-
OC6H4Cl)2.24 The C(4)−Cl(1)−Ru(1) angle (109.6(2)°) is
close to that (106.77(8)°) of complex 4.
Consistent with the solid-state structure, the 13C{1H} NMR
spectrum of 10 shows the Ru−CH signal as a triplet at 166.3
ppm with a JPC coupling constant of 8.7 Hz and that of Ru−
CHC as a singlet at 145.1 ppm. The CO signal was located at
204.1 ppm as a triplet with a JPC coupling constant of 16.9 Hz.
The 31P{1H} NMR spectrum shows two doublets at 32.58 and
29.07 ppm with a large coupling constant of 305.8 Hz.
Reported structurally characterized ruthenium haloarene
complexes include [Ru(PPh2CH2CH2PiPr2)(κO,κCl-
OC6Cl5)2],23 Ru3(CO)8(κO,κCl-OC6H4Cl)2,24 [CpRu(CO)-
(PPh3 )(p-IC6 H4 CH3 )]PF6 ,2 5 Ru(PPh3 )2 (κO,κBr-
OC6H2Br3)2,26 Ru(PMe2Ph)2(SC6F5)2(κS,κF-C6F5)27 and
[RuCl2 (PPh3 )(κP,κN,κF-PPh2 CH2 C(t Bu)NN
CHC6H3F2).28 We also noted that the reaction of the
ruthenium carbyne complex [Ru(CPh)ICl(CO)(PPh3)2)]+
with H2O was reported to give RuPhCl(CO)2(PPh3)2.1a
In summary, we have investigated the hydrolysis reactions of
MCl3(CCHC(o-ArCl)2)(PPh3)2 (M = Ru, Os), which
produced the interesting six-membered metallacycles MCl-
(κC,κCl-CHC(o-ArCl)2)(CO)(PPh3)2.
1
J(PP) = 275.8 Hz), 5.89 (d, J(PP) = 275.8 Hz). H NMR (400.13
MHz, CD2Cl2): δ 6.27 (dd, J(HH) = 8.0, 1.2 Hz, 1H, PhCl2), 6.40
(t, 1H, J(HH) = 8.0 Hz, PhCl2), 6.93 (dd, J(HH) = 8.0 Hz, 1H, 1.2 Hz,
PhCl2), 7.00 (t, J(HH) = 7.9 Hz, 1H, PhCl2), 7.21 (d, J(HH) = 7.9 Hz,
2H, PhCl2), 7.24−7.38 (m, 18H, PPh), 7.50−7.65 (m, 12H, PPh), 8.44
(t, J(PH) = 5.1 Hz, 1H, Os−CH). 13C{1H} NMR (100.62 MHz,
CD2Cl2): δ 180.0 (t, J(PC) = 11.7 Hz, Os(CO)), 158.1 (t, J(PC) = 5.5
Hz, Os−CH), 141.6 (s, Os−CHC), 138.4 (s, PhCl2), 133.8
(t, J(PC) = 5.1 Hz, PPh), 132.0 (s, PhCl2), 131.2 (t, J(PC) = 25.4
Hz, PPh), 129.3 (s, PPh), 127.7 (s, PhCl2), 127.3 (t, J(PC) = 5.0 Hz,
PPh), 125.8 (s, PhCl2), 125.7 (s, PhCl2), 125.5 (s, PhCl2). Anal. Calcd
for C51H37Cl5OOsP2: C, 55.93; H, 3.40. Found: C, 55.77; H, 3.48.
mer-OsCl3(CCHC(o-C6H4Cl)2)(PPh3)2 (5). This known com-
plex 512a was prepared by the following modified procedure. A mixture
of OsCl2(PPh3)3 (1.360 g, 1.30 mmol), HCCC(OH)(o-C6H4Cl)2
(8; 0.426 g, 1.54 mmol), HPPh3BF4 (1.001 g, 2.86 mmol), and NaCl
(1.236 g, 21.1 mmol) in CH2Cl2 (40 mL) was stirred for 48 h to give a
brownish green suspension. The solvent was removed completely
under vacuum, and the residue was extracted with benzene (30 mL × 3)
and the extract then filtered. The solvent of the extract was
removed under vacuum. The residue was dissolved in CH2Cl2 (8 mL).
Addition of diethyl ether (20 mL) gave a green precipitate and a
brown solution, which was separated by filtration. The solid was
washed with diethyl ether (20 mL × 2) and hexane (20 mL) and then
dried under vacuum to give 5 as a green solid. Yield: 0.711 g, 50.6%.
31P{1H} NMR (161.98 MHz, CD2Cl2): δ −14.2 (s). 1H NMR (400.13
MHz, CD2Cl2): δ 4.56 (t, J(PH) = 1.8 Hz, 1H, OsCCH), 6.74 (dd,
J(HH) = 7.9, 1.0 Hz, 1H, PhCl), 7.03 (dd, J(HH) = 7.9, 1.0 Hz, 1H,
PhCl), 7.15−7.28 (m, 4 H, PhCl), 7.28−7.38 (m, 19H, 18H for PPh
and 1H for PhCl), 7.41 (t, J(HH) = 7.6 Hz, 1H, PhCl), 7.73−7.82
(m, 12H, PPh). 13C{1H} NMR (100.62 MHz, CD2Cl2): δ 262.4 (t, J(PC) =
11.2 Hz, OsC), 156.1 (s, CHC(o-ClPh)2), 139.0 (s, CHC-
(o-ClPh)2), 137.8 (s, PhCl), 135.7 (s, PhCl), 134.4 (t, J(PC) = 5.0 Hz,
PPh), 132.8 (s, PhCl), 131.0 (s, PhCl), 130.9 (s, PhCl), 130.5
(s, PhCl), 130.1 (s, PhCl), 130.0 (s, PhCl), 129.9 (t, J(PC) = 26.2 Hz,
PPh), 129.8 (s, PhCl), 129.7 (s, PPh), 129.0 (s, PhCl), 127.4 (s, PhCl),
126.9 (t, J(PC) = 5.0 Hz, PPh), 126.3 (s, PhCl). Anal. Calcd for
C51H39Cl5OsP2: C, 56.65; H, 3.64. Found: C, 56.62; H, 3.75. Its
structure has been confirmed by X-ray diffraction. The molecular structure
is shown in Figure 4, and selected bond distances and angles are given in
Table 1.
EXPERIMENTAL SECTION
■
All manipulations were carried out under a nitrogen atmosphere using
standard Schlenk techniques unless otherwise stated. Solvents were
distilled under nitrogen from sodium benzophenone (hexane, ether,
THF) or calcium hydride (CH2Cl2). The propargyl alcohols were
prepared from the reactions of ethynylmagnesium bromide or LiC
CSiMe3 with related ketones, following a procedure similar to that for
the preparation of HCCC(OH)Ph2.29 OsCl2(PPh3)3 and
30
31
RuCl2(PPh3)3 were prepared according to the literature methods.
All other reagents were used as purchased from Aldrich Chemical Co.
Microanalyses were performed by M-H-W Laboratories (Phoenix,
1
AZ). H, 13C{1H}, and 31P{1H} NMR spectra were collected on a
1
Bruker ARX-400 spectrometer (400 MHz). H and 13C NMR shifts
are relative to TMS, and 31P chemical shifts are relative to 85% H3PO4.
mer-OsCl3(CCHC(o,o′-C6H3Cl2)2)(PPh3)2 (3). A mixture of
OsCl2(PPh3)3 (2.007 g, 1.91 mmol), HCCC(OH)(o,o′-C6H3Cl2)2
(2; 0.797 g, 2.30 mmol), HPPh3BF4 (1.348 g, 3.85 mmol), and NaCl
(1.376 g, 23.5 mmol) in CH2Cl2 (40 mL) was stirred for 48 h to give a
brownish green suspension. The solvent was removed completely
under vacuum, and the residue was extracted with benzene (30 mL × 3)
and then filtered. The solvent of the extract was removed under
vacuum. The residue was dissolved in CH2Cl2 (8 mL) and the solution
carefully layered with diethyl ether (60 mL). The mixture stood at
room temperature for 3 days to give green crystals with a brown
solution, which was separated by filtration. The solid was washed with
diethyl ether (20 mL × 2) and hexane (20 mL) and dried under
vacuum to give 3 as a green solid. Yield: 0.577 g, 26.2%. 31P{1H} NMR
(161.98 MHz, CD2Cl2): δ −12.1 (s). 1H NMR (400.13 MHz,
CD2Cl2): δ 4.81 (t, J(PH) = 2.1 Hz, 1H, OsCCH), 7.07−7.23 (m,
3H, PhCl2), 7.23−7.41 (m, 21H, 18H for PPh and 3H for PhCl2),
7.73−7.83 (m, 12H, PPh). 13C{1H} NMR (100.62 MHz, CD2Cl2): δ
259.6 (t, J(PC) = 10.8 Hz, OsC), 147.2 (s, OsC-CHC), 139.2
(s, PhCl2), 136.5 (s, OsCCHC), 134.7 (t, J(PC) = 4.9 Hz, PPh),
134.5 (s, PhCl2), 134.3 (s, PhCl2), 130.0 (s, PhCl2), 129.7 (s, PPh),
129.6 (s, PhCl2), 129.5 (t, J(PC) = 26.8 Hz, PPh), 128.6 (s, PhCl2),
OsCl(κC,κCl-CHC(o-C6H4Cl)2)(CO)(PPh3)2 (6). To a suspen-
sion of 5 (44 mg, 0.041 mmol) in THF (20 mL) was added H2O (0.2
mL, 11.1 mmol). The mixture was stirred at 50 °C for 22 h to give a
greenish-yellow solution. The solvent was removed completely under
vacuum, and the residue was loaded on a silica gel column that was
flashed with dichloromethane/hexane (v/v 1/5) and then eluted with
dichloromethane/hexane (v/v 5/1). The yellow band was collected.
The solvents were removed under vacuum to give 6 as a yellow solid.
Yield: 11 mg, 26.2%. Further eluting with diethyl ether gave a green
solid (26 mg) containing mainly the starting materials. 31P{1H} NMR
(161.98 MHz, CD2Cl2): δ 9.37 (d, J(PP) = 286.2 Hz), 4.41 (d, J(PP) =
1
286.7 Hz). H NMR (400.13 MHz, CD2Cl2): δ 6.44 (d, J(HH) =
8.0 Hz, 1H, PhCl), 6.50 (d, J(HH) = 7.8 Hz, 1H, PhCl), 6.54−6.61
(m, 2H, PhCl), 6.86 (t, J(HH) = 7.6 Hz, 1H, PhCl), 7.06−7.15 (m,
2H, PhCl), 7.20−7.41 (m, 19H, PhCl and PPh), 7.45−7.56 (m, 7H,
PPh and Os−CH), 7.65−7.78 (m, 6H, PPh). 13C{1H} NMR (100.62
MHz, CD2Cl2): δ 179.9 (t, J(PC) = 11.6 Hz, Os(CO)), 150.5
6162
dx.doi.org/10.1021/om200685v|Organometallics 2011, 30, 6159−6165

Organometallics
Article
filtered. The yellow solid was washed with diethyl ether (30 mL × 2)
again and dried under vacuum to give 9 as a yellow solid. Yield: 0.862
g, 68.8%. 31P{1H} NMR (161.98 MHz, CD2Cl2): δ 13.7 (s). 1H NMR
(400.13 MHz, CD2Cl2): δ 5.29 (t, J(PH) = 2.2 Hz, 1H, RuCCH),
6.74 (dd, J(HH) = 7.8, 1.2 Hz, 1H, PhCl), 7.03 (dd, J(HH) = 7.9, 1.0
Hz, 1H, PhCl), 6.95−7.40 (m, 25 H, 18 H for PPh and 7 H for PhCl),
7.80−7.90 (m, 12 H, PPh). Anal. Calcd for C51H39Cl5RuP2: C, 61.74;
H, 3.96. Found: C, 62.00; H, 4.18.
RuCl(κC,κCl-CHC(o-C6H4Cl)2)(CO)(PPh3)2 (10). To a suspen-
sion of 9 (150 mg, 0.151 mmol) in THF (20 mL) was added H2O
(0.2 mL, 11.1 mmol). The mixture was stirred at room temperature for
40 min to give a yellow solution. The solvent was removed completely
under vacuum, and the residue was loaded on a silica gel column that
was flashed with dichloromethane/hexane (v/v 1/5) and then eluted
with dichloromethane/hexane (v/v 5/1). The yellow band was
collected. The solvents were removed under vacuum to give 10 as a
yellow solid. Yield: 98 mg, 69.0%. 31P{1H} NMR (161.98 MHz,
CD2Cl2): δ 32.58 (d, J(PP) = 305.8 Hz), 29.07 (d, J(PP) = 306.1 Hz).
1H NMR (400.13 MHz, CD2Cl2): δ 6.39 (d, J(HH) = 8.0 Hz, 1H,
PhCl), 6.59−6.68 (m, 4H, PhCl and Ru−CH), 6.80−6.90 (m, 1H,
PhCl), 7.07−7.18 (m, 2H, PhCl), 7.20−7.43 (m, 20H, PhCl and PPh),
7.50−7.88 (m, 6H, PPh). 13C{1H} NMR (100.62 MHz, CD2Cl2): δ
204.1 (t, J(PC) = 16.9 Hz, Ru(CO)), 166.3 (t, J(PC) = 8.7 Hz, Ru−
CH), 145.1 (s, Ru−CHC), 139.2 (s, PhCl), 135.4 (s, PhCl), 133.7
(d(br), J(PC) ≈ 31.2 Hz, PPh), 132.4 (d(br), J(PC) ≈ 40.0 Hz, PPh),
131.7 (s, PhCl), 130.7 (d(br), J(PC) ≈ 39.4 Hz, PPh), 130.2 (s, PhCl),
129.2 (s, PhCl), 129.1 (s, PPh), 128.2 (s, PhCl), 127.2 (br, PPh), 127.1
(s, PhCl), 126.6 (s, PhCl), 126.3 (s, PhCl), 126.1 (s, PhCl), 125.3
(s, PhCl). Anal. Calcd for C51H39Cl3ORuP2: C, 65.36; H, 4.19. Found:
C, 65.22; H, 4.32.
Crystal Structure Analyses. Crystals were grown by slowly
evaporating the solvent from their saturated solutions. The crystals of
4 and 10 were from toluene and benzene, respectively, whereas those
of 3 and 5 were from dichloromethane/hexane. The diffraction
intensity data of 4 were collected with a Bruker Smart APEX CCD
diffractometer with graphite-monochromated Mo Kα radiation (λ =
0.710 73 Å). Lattice determination and data collection were carried out
using SMART v.5.625 software. Data reduction and absorption
correction by empirical methods were performed using SAINT v 6.26
and SADABS v 2.03, respectively. The diffraction intensity data of 3, 5,
and 10 were collected with an Oxford Diffraction Gemini S Ultra
Figure 4. ORTEP drawing of 5 with ellipsoids at the 35% probability
level. The hydrogen atoms on the PPh3 ligands are omitted for clarity.
(t, J(PC) = 6.2 Hz, Os−CH), 145.7 (s, Os−CHC), 139.7 (s, PhCl),
133.9 (d, J(PC) = 9.0 Hz, PPh), 133.5 (d, J(PC) = 9.1 Hz, PPh), 132.3
(d(br), J(PC) = 48.3 Hz, PPh), 132.0 (s, PhCl), 130.4 (s, PhCl), 130.2
(d(br), J(PC) = 47.2 Hz, PPh), 129.3 (s, PPh), 129.1 (s, PPh), 128.9
(s, PhCl), 128.1 (s, PhCl), 127.1 (d, J(PC) = 9.6 Hz, PPh), 126.9
(s, PhCl), 126.8 (s, PhCl), 126.2 (s, PhCl), 126.1 (s, PhCl), 124.8
(s, PhCl). Anal. Calcd for C51H39Cl3OOsP2: C, 59.68; H, 3.83. Found:
C, 59.52; H, 4.14.
mer-RuCl3(CCHC(o,o′-C6H4Cl)2)(PPh3)2 (9). To a mixture
of RuCl2(PPh3)3 (1.210 g, 1.26 mmol) and HCCC(OH)-
(o-C6H4Cl)2 (8; 0.440 g, 1.59 mmol) in CH2Cl2 (50 mL) was slowly
added hydrogen chloride (1.0 M in diethyl ether, 2.8 mL, 2.8 mmol).
The reaction mixture was stirred at room temperature for 2 h to give a
reddish yellow solution. Then it was filtered via a filter paper to
remove a small amount of purple precipitate. The volume of the
filtrate was reduced to ca. 5 mL under vacuum, and then diethyl ether
(50 mL) was slowly added with stirring to produce a yellow
precipitate. After the mixture was stirred for a further 20 min, it was
Table 3. Crystallographic Details for Complexes 3−5 and 10
3
4·C6H5CH3
5
10·3/2C6H6
C60H48Cl3ORuP2
empirical formula
C51H37Cl7OsP2
C58H45Cl5OOsP2
1187.33
C51H39Cl5OsP2
1081.21
formula wt
1150.10
1054.34
173(2)
1.541 78
triclinic
temp, K
298(2)
100(2)
173(2)
wavelength, Å
1.541 78
0.710 73
0.710 73
cryst syst
orthorhombic
triclinic
monoclinic
I2/a
space group
P212121
P1
P1
̅
̅
a, Å
10.3624(3)
10.2620(8)
25.295(2)
12.8976(7)
29.254(3)
90
11.4372(6)
12.3519(6)
18.4620(9)
108.436(5)
91.266(4)
b, Å
14.9316(7)
11.6363(10)
23.4763(19)
76.4000(10)
79.0880(10)
66.4540(10)
2483.5(4)
c, Å
29.4464(13)
α, deg
90
β, deg
90
112.843(10)
90
γ, deg
V, Å3
90
101.520(47)
2414.2(2)
4556.2(3)
8795.3(13)
8
Z
4
2
2
d(calcd), Mg/m3
θ range for data collecn, deg
no. of rflns collected
no. of indep rflns
no. of data/restraints/params
goodness of fit on F2
final R indices (I > 2σ(I))
largest diff peak and hole, e Å−3
1.677
1.588
1.633
1.450
5.39−67.49
23 919
1.80−27.00
27 519
2.56−26.00
33 708
4.90−66.60
11 926
8139 (R(int) = 0.0559)
8139/0/551
10 625 (R(int) = 0.0260)
10 625/0/605
1.043
8578 (R(int) = 0.1069)
8578/0/532
1.008
7658 (R(int) = 0.0505)
7658/66/604
1.033
1.005
R1 = 0.0274, wR2 = 0.0515
0.838 and −0.463
R1 = 0.0232, wR2 = 0.0545
1.316 and −0.621
R1 = 0.0565, wR2 = 0.0737
2.235 and −1.942
R1 = 0.0627, wR2 = 0.1506
1.815 and −0.809
6163
dx.doi.org/10.1021/om200685v|Organometallics 2011, 30, 6159−6165

Organometallics
Article
X-ray diffractometer. Monochromated Cu Kα radiation (λ = 1.541 78 Å)
was used for 3 and 10, and monochromated Mo Kα radiation (λ =
1.541 78 Å) was used for 5. Lattice determination, data collection, and
reduction were carried out using CrysAlisPro 171.33.46. Absorption
correction was performed using SADABS built into the CrysAlisPro
program suite. Structure solution and refinement for all compounds
were performed using the Olex2 software package32 (with embedded
SHELXTL33). All the structures were solved by direct methods,
expanded by difference Fourier syntheses, and refined by full-matrix
least squares on F2. Compound 3 crystallizes in chiral space group
P212121, but crystals showed considerable racemic twinning (the minor
component was refined to 45.3%). All non-hydrogen atoms were
refined anisotropically with a riding model for the hydrogen atoms,
except as noted separately. Further details on crystal data, data
collection, and refinement are summarized in Table 3.
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ASSOCIATED CONTENT
* Supporting Information
■
A. M.; Onate, E.; Royo, E. Organometallics 2004, 23, 3021−3030.
̃
S
(k) Wen, T. B.; Hung, W. Y.; Zhou, Z. Y.; Lo, M. F.; Williams, I. D.;
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Z. Y.; Lo, M. F.; Williams, I. D.; Jia, G. Organometallics 2003, 22,
CIF files giving X-ray crystallographic data for 3 (CCDC
835113), 4 (CCDC 835114), 5 (CCDC 835115), and 10
(CCDC 835116). This material is available free of charge via
the Internet at http://pubs.acs.org.
5217−5225. (m) Castarlenas, R.; Esteruelas, M. A.; Onate, E.
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Organometallics 2001, 20, 3283−3292. (n) Baya, M.; Crochet, P.;
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Esteruelas, M. A.; Gutierrez-Puebla, E.; Lopez, A. M.; Modrego, J.; Onate,
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AUTHOR INFORMATION
Corresponding Author
*E-mail: chjiag@ust.hk.
■
́
́ ́
Esteruelas, M. A.; Garcia-Yebra, C.; Gutierrez-Puebla, E.; Olivan, M.
Organometallics 2000, 19, 2184−2193. (p) Wen, T. B.; Cheung, Y. K.;
Yao, J.; Wong, W. T.; Zhou, Z. Y.; Jia, G. Organometallics 2000, 19,
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ez, A. M.; Martinez,
3803−3809. (q) Crochet, P.; Esteruelas, M. A.; Lop
M. P.; Olivan, M.; Onate, E.; Ruiz, N. Organometallics 1998, 17, 4500−
4509. (r) Crochet, P.; Esteruelas, M. A.; Lop
Organometallics 1998, 17, 3479−3486. (s) Esteruelas, M. A.; Lop
ACKNOWLEDGMENTS
́
̃
■
́
ez, A. M.; Ruiz, N.; Tolosa, J. I.
ez,
This work was supported by the Hong Kong Research Grant
Council (Project No. HKUST 601007, 601408, HKUST18/
CRF/08).
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A. M.; Ruiz, N.; Tolosa, J. I. Organometallics 1997, 16, 4657−4667.
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