Reactions of [RuClH(CO)(PPh3)3] with 2-methyl-2-propen-1-ol. Reversible insertion/β-elimination, and reductive elimination on a 3-hydroxy-2-methylpropyl-C1,O-ruthenium(II) complex

Article abstract of DOI:10.1016/S0022-328X(98)00932-2

A hydridoruthenium complex [RuClH(CO)(PPh₃)₃] (1) reacts with 2-methyl-2-propen-1-ol at room temperature to give an insertion product, [Ru{CH₂CH(CH₃)CH₂OH}Cl(CO)(PPh ₃)₂] (2), which undergoes β-elimination of 2-methyl-2-propen-1-ol reversibly in solution. The complex 1 reacts with 2-methyl-2-propen-1-ol under benzene refluxing conditions to produce 2-methylpropan-1-ol, 2-methylpropanal and 2-methyl-2-propenal catalytically in the presence of water. The production of 2-methylpropanal results in formation of two isomers of 2-methylpropanoato complex [RuCl{η²-(CH₃)₂CHCO ₂}(CO)(PPh₃)₂] (3). Heating 1 at 80°C in neat 2-methyl-2-propen-1-ol affords a novel ruthenium(O) complex [Ru{η⁴-CH₂=C(CH₃)CHO}-(CO)(PPh ₃)₂] (7) and a quaternary phosphonium salt [Ph₃PCH₂CH(CH₃)CH₂OH]Cl (8) via reductive elimination of 3-chloro-2methylpropan-1-ol from 2. The molecular structures of 7 and 8 are determined by X-ray crystallography.

Full text of DOI:10.1016/S0022-328X(98)00932-2

Journal of Organometallic Chemistry 574 (1999) 121–132
Reactions of [RuClH(CO)(PPh3)3] with 2-methyl-2-propen-1-ol.
Reversible insertion/i-elimination, and reductive elimination on a
3-hydroxy-2-methylpropyl-C1,O-ruthenium(II) complexꢀ
Katsuma Hiraki a,*, Akihiro Nonaka a, Takahiro Matsunaga a, Hiroyuki Kawano b
a Department of Applied Chemistry, Faculty of Engineering, Nagasaki Uni6ersity, Bunkyo-machi, Nagasaki 852-8521, Japan
b Graduate School of Marine Science and Engineering, Nagasaki Uni6ersity, Bunkyo-machi, Nagasaki 852-8521, Japan
Received 26 June 1998
Abstract
A hydridoruthenium complex [RuClH(CO)(PPh3)3] (1) reacts with 2-methyl-2-propen-1-ol at room temperature to give an
insertion product, [Ru{CH2CH(CH3)CH2OH}Cl(CO)(PPh3)2] (2), which undergoes i-elimination of 2-methyl-2-propen-1-ol
reversibly in solution. The complex 1 reacts with 2-methyl-2-propen-1-ol under benzene refluxing conditions to produce
2-methylpropan-1-ol, 2-methylpropanal and 2-methyl-2-propenal catalytically in the presence of water. The production of
2-methylpropanal results in formation of two isomers of 2-methylpropanoato complex [RuCl{p2-(CH3)2CHCO2}(CO)(PPh3)2] (3).
Heating 1 at 80°C in neat 2-methyl-2-propen-1-ol affords a novel ruthenium(O) complex [Ru{p4-CH2ꢀC(CH3)CHꢁO}-
(CO)(PPh3)2] (7) and a quaternary phosphonium salt [Ph3PCH2CH(CH3)CH2OH]Cl (8) via reductive elimination of 3-chloro-
2methylpropan-1-ol from 2. The molecular structures of 7 and 8 are determined by X-ray crystallography. © 1999 Elsevier Science
S.A. All rights reserved.
Keywords: [RuClH(CO)(PPh3)3]; Reversible insertion; Reductive elimination
1. Introduction
hydridoruthenium complexes and the allylic alcohols is
needed to figure out how the ruthenium-complex cata-
lysts work.
A large number of ruthenium complex-catalyzed re-
actions of allylic alcohols have been reported, such as
isomerization of allylic alcohols [1–4] and ethers [5–7],
redox fragmentation of allylic ethers [8], reshuffling of
allylic alcohols [9], and condensation of allylic alcohols
and 1-alkynes [10]. Hydridoruthenium complexes play
essential roles in these catalytic reactions through coor-
dination, activation, and transformation of the allylic
alcohols on the ruthenium center. Therefore, detailed
investigation on ruthenium species derived from the
We have been working on reactions of a hydri-
doruthenium(II) complex [RuClH(CO)(PPh3)3] (1) and
some allylic compounds such as allyl sulfides [11] and
allylamines [12]. The allylic compounds generally in-
serted into the Ru–H bond of 1 to give the correspond-
ing five-membered chelate rings. Sometimes the
carbon–heteroatom bonds were cleaved; the allyl
sulfides gave thiolato-bridged binuclear complexes ac-
companied by the liberation of propene [11]. The ter-
tiary allylamines, in contrast, gave a y-allylruthenium
complex in which the allyl moiety of the allylamines
was combined to the ruthenium [12]. Here we report
our recent study on reaction of the hydridorutheniu-
m(II) complex 1 to 2-methyl-2-propen-1-ol (a 2-substi-
tuted allyl alcohol). Instead of the carbon–heteroatom
ꢀ A contribution to the special issue of the Journal of
Organometallic Chemistry for a memorial to the late Professor
Rokuro Okawara.
* Corresponding author. Tel.: +81-95-847-1111; fax: +81-95-847-
6749; e-mail: hirokwn@net.nagasaki-u.ac.jp.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(98)00932-2

122
K. Hiraki et al. / Journal of Organometallic Chemistry 574 (1999) 121–132
bond cleavage, unexpected reductive elimination of 3-
chloro-2-methyl-2-propan-1-ol follows the insertion of
3-hydroxy-2-methylpropyl-C1,O-ligand. The 1H-NMR
spectrum of the precipitates shows a doublet of the
methyl protons at l 0.35 and five broad signals of the
methylene and methine protons in the range of l
the allylic moiety to give
a
novel (p4-
enone)ruthenium(O) complex and a quaternary phos-
phonium salt. Furthermore, in the presence of water,
carboxylato species, 2-methylpropanoatoruthenium(II)
complexes are derived from 1 and 2-methyl-2-propen-1-
ol.
1.4–3.2,
which
were
ascribed
to
the
1
‘RuCHaHbCH(CH3)CHcHdO’ moiety by means of H-
1H-COSY. These spectroscopic data confirm the struc-
ture of 2 depicted in Scheme 1.
When the solution of the precipitates stands at room
1
temperature, the 31P{1H}- and H-NMR spectra indi-
2. Results and discussion
cate a gradual increase of the starting complex 1. In
addition, the H-NMR shows four signals assignable to
1
2.1. Insertion of 2-methyl-2-propen-1-ol: formation of
3-hydroxy-2-methylpropyl-C1,O-ruthenium(II) complex
2-methyl-2-propen-1-ol. These results are interpreted
together in the following manner: in the presence of an
excess amount of 2-methyl-2-propen-1-ol, the allylic
moiety inserts into the Ru–H bond to give 2, whereas
in the absence of 2-methyl-2-propen-1-ol, the allylic
alcohol is gradually eliminated from the complex 2.
As shown above, the insertion/i-elimination of 2-
methyl-2-propen-1-ol on the ruthenium(II) center are
reversible. In our previous study [11,12], alkyl allyl
sulfides, primary and secondary allylamines irreversibly
inserted into the Ru–H bond of 1. Basicity of the
heteroatom function explains the difference between
2-methyl-2-propen-1-ol and the other allylic com-
pounds. The alcoholic hydroxy function of 2-methyl-2
propen-1-ol is a weak and hard base so that the hy-
droxy group is coordinated weakly to the ruthenium(II)
center, a soft acid. That is, the 3-hydroxy-2-methyl-
propyl-C1,O-ruthenium(II) five-membered chelate is
rather unstable in comparison with 3-(alkylmercapto)-
propyl-C1,S- and 3-amino- or 3-(alkylamino)pro-
pyl-C1,N-chelate structures. Because of the weak coor-
dination of the hydroxy group, the ruthenium(II)
center easily dissociates the hydroxy group to
When the hydridoruthenium(II) complex 1 is heated
with a large excess amount of 2-methyl-2-propen-1-ol in
benzene at room temperature for 120 h, the starting
suspension turns into a yellow solution. The GLPC
analysis of the reaction mixture shows no peak other
than 2-methyl-2-propen-1-ol and benzene. Addition of
hexane to the concentrated reaction mixture gives pale
yellow precipitates of
a crude insertion product
[Ru{CH2CH(CH3)CH2OH}Cl(CO)(PPh3)2] (2). The in-
frared spectrum of the precipitates shows a strong band
at 1890 cm−1 and a broad band near 3520 cm−1
,
ascribable to w(CꢁO) and w(O–H), respectively. The
31P{1H}-NMR spectrum of the precipitates at −30°C
exhibits two doublets at l 34.8 and 42.6 with a remark-
ably large coupling constant (JPP=332.1 Hz) accompa-
nied by a set of the signals of 1, a triplet at l 11.1 and
a doublet at l 39.0. The doublets with the large cou-
pling constant are ascribed to two trans-coordinated
triphenylphosphines in different chemical circumstances
owing to a newly formed asymmetric carbon of the
Scheme 1. Products of reactions of 2-methyl-2-propen-1-ol with 1 under various conditions.

K. Hiraki et al. / Journal of Organometallic Chemistry 574 (1999) 121–132
123
with cyclohexanecarbaldehyde, benzaldehyde and 3-
phenylpropanal to give the corresponding carboxylato
complexes,
P,P%-trans-[RuCl(p2-RCO2)(CO)(PPh3)2]
(4–6a) and P,P%-cis-[RuCl(p2-RCO2)(CO)(PPh3)2] (4–
6b) (4a,b: R=C6H11; 5a,b: R=C6H5; 6a,b: R=
C6H5C2H4). These carboxylato complexes 4–6a,b are
identified by comparing their NMR spectra to those of
the authentic samples derived from 1 and the carboxylic
acids [13].
A considerable amount of 3-phenylpropan-1-ol is
formed along with the carboxylato complexes 6a and 6b
when the complex 1 reacts with 3-phenylpropanal start-
ing with an initial ratio of 1:2.2, respectively. The
GLPC analysis shows that a small amount of the
starting aldehyde remains (1/5–1/6 of 3-phenylpropan-
1-ol) and a trace amount of 3-phenylpropanoic acid is
free in the reaction mixture. No other organic product
is recognized. The formation of the alcohol and the
carboxylato complexes from the aldehyde reminds us of
the well known Cannizzaro reaction in the presence of
aqueous base [15]. This ruthenium-promoted reaction is
apparently not a mere Cannizzaro reaction because
even the aldehydes with an h-hydrogen give their corre-
sponding alcohols. This ruthenium-promoted Canniz-
zaro-type reaction is formulated as the following:
Fig. 1. Reaction time-conversion/yield curves of 2-methyl-2-propen-1-
ol (ꢁ) and its derivatives: 2-methylpropanal (ꢂ), 2-methylpropan-1-
ol (ꢃ) and 2-methylpropenal (ꢄ).
produce a vacant site. The vacant site abstracts a
i-hydrogen from the 3-hydroxy-2-methylpropyl ligand
to bring about the i-elimination of 2-methyl-2-propen-
1-ol.
2.2. Reaction of 1 with 2-methyl-2-propen-1-ol in the
presence of water
[RuClH(CO)(PPh3)3]+3RCHO+H2O
When 2-methyl-2-propen-1-ol is employed as pur-
chased (i.e. the presence of a small amount of water), 1
reacts with the allylic alcohol to give unexpected 2-
methylpropanoatoruthenium(II) complexes, P,P%-trans-
“P,P%-trans- and cis-[RuCl(p2-RCO2)(CO)(PPh3)2]
+PPh3+2RCH2OH
(1)
[RuCl{p2-(CH3)2CHCO2}(CO)(PPh3)2]
(3a)
and
There has previously been reported some other exam-
ples of ruthenium-promoted conversion of an aldehyde
into a coordinating carboxylate. Cook et al. [16]
P,P%-cis-[RuCl{p2-(CH3)2CHCO2}(CO)(PPh3)2] (3b) in
refluxing benzene (Scheme 1). Each complex is isolated
by purification on a silica-gel column chromatography.
The data of the elemental analyses, and the IR and
NMR spectroscopic analyses of 3a and 3b are consis-
tent with the P,P%-trans- and cis-structures, respec-
tively, and are identical with those of the corresponding
reported
that
[Ru2(OH)3(p6-C6Me6)2]PF6
and
[Ru2Cl4(p6-p-cymene)2] catalyzed disproportionation
of acetaldehyde into ethanol and acetic acid in the
presence of water, and that the former complex
was
recovered
as
a
carboxylato
complex,
authentic samples derived from
propanoic acid [13].
1
and 2-methyl-
[Ru2(OAc)3(p6-C6Me6)2]PF6. Ito et al. [17] reported that
[RuH2(PPh3)4] reacted with butanal in the presence of
The production of the carboxylato complexes is
caused by an aldehyde formed catalytically in the reac-
tion mixture. The GLPC analysis of the reaction mix-
ture reveals the catalytic conversion of the starting
2-methyl-2-propen-1-ol into 2-methylpropan-1-ol, 2-
methylpropanal and 2-methyl-2-propenal. Typical time-
conversion/yield curves of these compounds are shown
in Fig. 1. Isomerization of 2-methyl-2-propen-1-ol into
2-methylpropanal catalyzed by 1 is known [14], whereas
2-methylpropan-1-ol and 2-methyl-2-propenal are con-
sidered as disproportionation products of 2-methyl-2-
propen-1-ol via catalytic transfer hydrogenation. In the
presence of water, 1 reacts with 2-methylpropanal un-
der the benzene-reflux conditions to give the carboxy-
lato complexes 3a and 3b. In a similar manner, 1 reacts
water at 0°C to afford a carboxylato complex,
[RuH(C3H7CO2)(PPh3)3], which reacted with extra alde-
hyde molecules at over 75°C to give mono- and dicar-
bonyl dicarboxylato complexes, [Ru(C3H7CO2)2(CO)-
(PPh3)2] and [Ru(C3H7CO2)2(CO)2(PPh3)2].
In the literature, Cook et al. [16] proposed two
reaction paths for the catalytic disproportionation of
aldehyde; oxidative addition of the RC(O)–H bond of
the aldehyde and hydroxy-metallation on the CꢀO moi-
ety of the aldehyde followed by i-hydrogen elimina-
tion. As for our reaction, both the starting 1 and the
produced carboxylato complexes hold the carbonyl lig-
and, which generally stabilizes a low valent state but
unstabilizes a high valent state such as ruthenium(IV).
Accordingly, the hydroxy-ruthenation path is plausible

124
K. Hiraki et al. / Journal of Organometallic Chemistry 574 (1999) 121–132
for our ruthenium-promoted Cannizzaro-type reaction
of the aldehydes into the carboxylato complexes and
the alcohols.
whereas the presence of benzene retards the reaction.
Reaction rate decreases as the ratio of alcohol/1 in
benzene is reduced.
Taking this discussion into consideration, we propose
a mechanism for the formation of the carboxylato
complexes 3a,b as shown in Scheme 2. Isomerization of
2-methyl-2-propen-1-ol into 2-methylpropanal via an
olefin-inserted intermediate is a known process [2]. In-
sertion of the aldehyde into the Ru–H bond followed
by proton-transfer from the coordinating water to the
alkoxy ligand gives a hydroxyruthenium species and
one molecule of the alcohol. The hydroxy-ruthenation
of the second aldehyde occurs successively. The i-hy-
drogen elimination transfers the hydrogen to the third
aldehyde and, finally, the hydroxy proton migrates onto
the alkoxy ligand to produce the second alcohol
molecule and the carboxylato ligand.
2.4. Molecular structure of the (p4-enone)ruthenium(O)
complex 7
The NMR spectroscopic characteristics of 7, i.e. the
small JPP value and the unusual high-field shift of vinyl
protons, are common to some reported (p4-
enone)ruthenium(O) complexes [18,19]. A 13C-doublet
at l 39.7 coupled with a phosphorus atom is attributed
to the terminal methylene carbon showing an appropri-
ate J value (JCP=31.3 Hz). This confirms the p4-coor-
dination of the 2-methylpropenal moiety. These
spectroscopic data of 7 are consistent with the structure
having an p4-2-methylpropenal ligand, two phosphines
and one carbonyl group around the ruthenium(O) cen-
ter. To our knowledge, 7 is one of the rare examples of
(p4-enone)ruthenium(O) complexes having two phos-
phine and one CO ligands. Only Mawby and collabora-
tors [19] has prepared a series of p4-vinyl ketone
complexes [Ru{p4-RCHꢀCHC(C6H4X-4)ꢀO}(CO)(P-
2.3. Reaction of 1 with 2-methyl-2-propen-1-ol at a
high temperature
When the complex 1 is heated at 80°C for 48 h in
dried 2-methyl-2-propen-1-ol, 1 is converted into an
(p4-enone)ruthenium(O) complex [Ru{p4CH2ꢀC(CH3)
CHꢀO}(CO)(PPh3)2] (7) and a quaternary phospho-
nium salt [Ph3PCH2CH(CH3)CH2OH]Cl (8) almost
quantitatively (Scheme 1). The 31P{1H}-NMR spectrum
of the reaction mixture shows two doublets with a small
coupling constant (JPP=2.0 Hz) at l 31.0 and 40.7,
which are ascribed to 7, and another singlet of 8 at l
21.2 in a intensity ratio of nearly 1:1:1. These products
are isolated from the reaction mixture by silica-gel
column chromatography. The p4-enone complex 7 is
eluted with hexane–diethyl ether (1:2) in 68% yield. The
other product, the quaternary phosphonium salt 8 is
eluted with chloroform–methanol (4:1) in 48% yield.
Interestingly, the yields of 7 and 8 are significantly
dependent on the solvent and on the ratio of the
alcohol to 1, as shown in Table 1. The conversion of 1
to 7 and 8 is almost quantitative in the neat alcohol,
R%) ] (R=Ph, C(CH3)3, CH3 and H; X=H, Cl, CH3
3 2
and OCH3; PR% =P(CH3)2Ph, P(CH3)3, P(OCH3)2Ph)
3
by intramolecular combination of vinyl, aryl and car-
bonyl ligands in the ruthenium(II) complexes; but their
X-ray structures have not been published. Therefore we
tried the X-ray analysis on the (p4-enone)ruthenium(O)
complexes 7 having two phosphines and one carbonyl
group.
The X-ray structure of 7 is depicted in Fig. 2. The
selected bond distances and bond angles are summa-
rized in Table 2. As expected, the structure of 7 is
tripodal piano stool-like with the p4-2-methylpropenal
moiety; the bond lengths between the ruthenium atom
and the atoms of the coordinating 2-methylpropenal
˚
fall within 2.165(5)–2.208(5) A. The C(2)–C(3) length
˚
is 1.416(8) A and shorter than a normal C–C single
Scheme 2. A plausible mechanism for the formation of the carboxylato complexes in the presence of water. 3a,b: R=CH(CH3)2; 4a,b: R=C6H11
5a,b: R=C6H5; 6a,b: R=C6H5C2H4.
;

K. Hiraki et al. / Journal of Organometallic Chemistry 574 (1999) 121–132
125
Table 1
Effect of the ratio of 2-methyl-2-propen-1-ol to 1a
Run
1 (mg)
Ratio of alcohol/1
Benzene (ml)
Time (h)
Yields (%)b
7
8
Free PPh3
1c
2
3
4
5
600
300
100
100
100
190
200
100
25
–
5
10
10
10
48
24
48
48
48
99
41
16
12
5
83
44
12
Trace
Trace
Trace
Trace
Trace
26
5
38
a Reactions are carried out under benzene-refluxing conditions unless otherwise stated.
b Yields are calculated based on the integrated intensities of the 31P-NMR peaks.
c Reaction is carried out at 80°C (see Section 3).
˚
bond length, whereas the C(3)ꢀC(4) length is 1.420(9) A
and longer than that of a normal CꢀC bond [20].
Especially, the C(2)–C(3) and C(3)ꢀC(4) distances are
almost the same within an error. Therefore the 2-
methylpropenal moiety apparently bears delocalized y-
electrons being coordinated in p4-mode. These
structural characteristics are quite similar to another
2-methyl-2-propen-1-ol with the aid of an acid can be
denied [21].
Thc detailed 31P{1H}-NMR analysis reveals that the
insertion of 2-methyl-2-propen-1-ol occurs before the
formation of 7 and 8 (Fig. 4). When the reaction
mixture is kept at room temperature for 72 h, the
insertion product 2 is produced in the mixture along
with the starting 1 in a ratio of 3:10, respectively. After
heating at 50°C for an additional 48 h, the ratio of 1:2
changes slightly to 4:10 and three 31P-signals are ob-
served at l 21.2 (8), and 31.0 and 40.7 (7). Further-
more, the extra treatment of the mixture at 65°C for 70
h makes the products 7 and 8 dominant, whereas 1 and
2 disappear completely.
Based on these results, a reasonable route to generate
a ruthenium(O) species is reductive elimination of 3-
chloro-2-methylpropan-1-ol after the insertion of 2-
methyl-2-propen-1-ol [22]. As shown in Scheme 3, the
starting 2-methyl-2-propen-1-ol is catalytically con-
verted into 2-methylpropenal during the reaction. Once
the unsaturated ruthenium(O) species is generated, it
has to be trapped by 2-methylpropenal to form 7.
(p4-enone)ruthenium(O)
complex,
[Ru(CH3COCHꢀCHPh)(CO)2(PPh3)] that has one
phosphine and two CO ligands [18].
2.5. Characterization of the phosphonium chloride 8
The analytical and NMR spectroscopic data of 8 are
consistent with the structure that is confirmed by single
crystal X-ray analysis (Fig. 3). The selected bond dis-
tances and bond angles are summarized in Table 3. The
quaternary phosphorus is attached to the terminal car-
bon of the 2-methyl-2-propen-1-ol, whereas the hydro-
gen is bound to the inner carbon making an asymmetric
center. Four P–C bond distances are almost similar to
˚
one another (1.798 A average) and fall within the range
of those of [Et3PCMe2OH]Br and a zwitterionic phos-
phonium salt (MeO)CH(Ph)P+Ph2(C6H4SO3−) re-
ported so far [21]. The Cl(1)···O(1) distance is 3.076(4)
Reaction of
a
dihydridoruthenium(II) complex
[RuH2(CO)(PPh3)3] with 2-methylpropenal in refluxing
toluene results in the formation of 7 [23]. The result
confirms that the p4-enone complex 7 arises when the
ruthenium(O) species generated in situ [24] comes in
contact with 2-methylpropenal. As to the released alkyl
chloride, 3-chloro-2-methylpropan-1-ol reacts with the
free PPh3 to give 8.
Castano et al. [25] reported that the closely
related phosphonium salt [Ph3PCHꢀCHCO2CH3]Cl
was formed in the reaction of 1 with methyl pro-
piolate. They supposed that the direct reaction
between the terminal alkyne and triphenylphos-
phine gave an alkenylphosphonium acetylide and
that the substitution of the acetylide anion for
the chloride ligand of an unidentified insertion
˚
A and it is reasonable to expect a hydrogen bond
between the chloride anion and the alcoholic OH group
in the solid state. In contrast, there is no close contact
between the positively charged phosphorus atom and
the negative centers such as Cl and O; all the distances
between the phosphorus and those negative atoms are
˚
longer than 3.60 A, showing negligible electrostatic
attraction between them.
2.6. Mechanism of the formation of 7 and 8
The ruthenium complex is essential to the formation
of 8. Actually, reaction between PPh3 and an excess
amount of aqueous HCl in refluxing 2-methyl-2-
propen-1-ol without 1 affords no quaternary phospho-
nium salt. Hence a direct reaction of PPh3 and
product
[Ru(CHꢀCHCO2CH3)Cl(CO)(PPh3)2]
fol-
lowed to give the isolable product [Ru(CHꢀCHCO2
CH3)(CꢁCCO2CH3)Cl(CO)(PPh3)2].

126
K. Hiraki et al. / Journal of Organometallic Chemistry 574 (1999) 121–132
Fig. 2. Molecular structure of 7 showing the atom numbering scheme. Hydrogen atoms are omitted for clarity.
From our viewpoint, however, this formation of the
alkenylphosphonium salt can be attributed to the result
of the reductive elimination of methyl i-chloroacrylate.
The reductive elimination is accompanied by the forma-
tion of the unsaturated ruthenium(O) species. When the
ruthenium(O) species is formed, oxidative addition of
the terminal C–H bond of the alkyne readily occurs on
the ruthenium(O) center to give an alkynyl(hy-
drido)ruthenium(II) species. Successive insertion of the
alkyne into the Ru–H bond forms the final product
[Ru(CHꢀCHCO2CH3)(CꢁCCO2CH3)Cl(CO)(PPh3)2].
Therefore, the formation of the ruthenium(O) species in
the presence of the alkyne can be overlooked.
Our plausible mechanism explains well the regioselec-
tive formation of 8. The structure of 8 in which the
terminal carbon is attached to the phosphorus must be
derived from 3-chloro-2-methylpropan-1-ol, an anti-
Markownikov adduct of HCl and 2-methyl 2-propen-1-
ol. The simple reductive elimination from the insertion
product 2 affords the anti-Markownikov adduct in a
single step. If HCl is added directly to 2-methyl-2-
propen-1-ol, the addition should obey Markownikov
rule to give 2-chloro-2-methylpropan-1-ol. It could only
afford [Ph3PC(CH3)2CH2OH]Cl, an isomer of 8.
is generated, because the reductive elimination proceeds
rather slower than the catalytic reactions. When the
reaction is carried out in the neat alcohol, the amount
of alcohol is large enough for all the starting 1 to be
converted into the ruthenium(O) species 7 (and also its
accompanying product 8) via the slow reductive
elimination.
In this mechanism, the alkylchlororuthenium(II) spe-
cies 2 releases the alkyl chloride in the presence of
tertiary phosphine to afford ruthenium(O) species and
alkylphosphonium chloride. From the viewpoint of the
catalytic process, most of previous studies on the
chlorohydridoruthenium(II) complex 1 have mentioned
i-elimination from the insertion products [26], but
Table 2
˚
Selected bond distances (A), bond angles (°), and torsion angles (°)
for 7
Bond distances
Ru(1)–P(1)
Ru(1)–C(1)
Ru(1)–C(3)
Ru(1)–O(2)
O(2)–C(2)
C(3)–C(4)
2.364(1) Ru(1)–P(2)
1.830(5) Ru(1)–C(2)
2.208(5) Ru(1)–C(4)
2.169(4) O(1)–C(1)
1.321(7) C(2)–C(3)
1.420(9) C(3)–C(5)
2.360(1)
2.165(5)
2.192(6)
1.152(6)
1.416(8)
1.508(8)
This mechanism also explains the decrease in the
yield of 7 as reducing the ratio of alcohol/1 in benzene
shown in the runs in Table 1. Scheme 3 implies that the
catalytic isomerization and/or transfer hydrogenation
and the formation of the ruthenium(O) species con-
sume the 2-methyl-2-propen-1-ol competitively. When
the ratio of alcohol/1 is small, most of the alcohol must
be consumed by the catalytic isomerization and/or
transfer hydrogenation before the ruthenium(O) species
Bond angles
P(1)–Ru(1)–P(2)
P(2)–Ru(1)–C(1)
O(2)–C(2)–C(3)
C(2)–C(3)–C(5)
103.99(5) P(1)–Ru(1)–C(1)
96.7(2) Ru(1)–C(1)–O(1)
118.2(5) C(2)–C(3)–C(4)
118.9(6) C(4)–C(3)–C(5)
91.0(2)
175.4(5)
115.3(5)
125.3(6)
Torsion angles
O(2)–C(2)–C(3)–C(4)
3.2(7) O(2)–C(2)–C(3)–C(5) 175.6(5)

K. Hiraki et al. / Journal of Organometallic Chemistry 574 (1999) 121–132
127
Fig. 3. Molecular structure of 8 showing the atom numbering scheme. Hydrogen atoms arc omitted for clarity.
rarely reductive elimination. Our case is the first exam-
ple that confirms the reductive elimination of the alkyl
chloride forming the ruthenium(O) species.
Complex 1 was prepared according to the literature
[27]. Dried 2-methyl-2-propen-1-ol was distilled slowly
after careful treatment with a small amount of sodium.
All the aldehydes and the carboxylic acids were used as
purchased. Solvents were dried with usual methods and
distilled prior to use.
3. Experimental details
All the reactions were carried out by means of the
ordinary Schlenk-tube techniques under a nitrogen at-
mosphere. However, special precautions were taken to
exclude air and moisture during the column-chromatog-
raphy process and the spectroscopic measurements,
since most of the complexes were air-stable as solids
and stable for a short period in solution.
Table 3
˚
Selected bond distances (A) and angles (°) for 8
Bond distances
P(1)–C(1)
P(1)–C(20)
C(1)–C(2)
C(2)–C(4)
1.798(5) P(1)–C(10)
1.789(5) P(1)–C(30)
1.545(7) C(2)–C(3)
1.515(8) C(3)–O(1)
1.789(5)
1.799(4)
1.518(8)
1.426(7)
IR spectra were recorded on a JASCO A-100 spec-
trophotometer with KBr disks. GLPC analyses were
carried out on a Hitachi model 263-30 equipped with a
flame ionization detector and a 5 mm¥×3 m stainless-
steel column (SE-30 or PEG 20M). Elemental analyses
Bond angles
1
and NMR (400 MHz for H, 101 MHz for 13C and 162
C(1)–P(1)–C(10)
C(1)–P(1)–C(30)
C(10)–P(1)–C(30)
P(1)–C(1)–C(2)
C(1)–C(2)–C(4)
C(2)–C(3)–O(1)
108.1(2)
C(1)–P(1)–C(20)
C(10)–P(1)–C(20)
C(20)–P(1)–C(30)
C(1)–C(2)–C(3)
C(3)–C(2)–C(4)
111.6(2)
MHz for 31P) measurements were carried out at the
Center for Instrumental Analysis, Nagasaki University,
with a Yanaco MT-3 CHN Corder and a JEOL GX-
400 spectrometer, respectively. Single crystal X-ray
structure analyses were performed at the same institute.
111.9(2)
106.4(2)
118.7(3)
110.5(5)
113.9(5)
109.7(2)
109.0(2)
110.1(4)
110.4(5)

128
K. Hiraki et al. / Journal of Organometallic Chemistry 574 (1999) 121–132
Fig. 4. Time-programmed 31P{1H}-NMR spectra of the reaction of 1 with neat 2-methyl-2-propen-1-ol: (a) after 72 h at room temperature; (b)
after the treatment at 50°C for an additional 48 h (total 120 h); (c) after an extra 70 h at 65°C (total 190 h).
3.1. Reaction of 1 with 2-methyl-2-propen-1-ol at
room temperature
to give yellow solids of [Ru{CH2CH(CH3)CH2OH}Cl
(CO)(PPh3)2] (2) (112 mg, 74%). Anal. Found: C, 65.24;
H, 5.32. Calc. for C41H39ClO2P2Ru: C, 64.61; H, 5.16%.
M.p. 166°C (dec.). IR (cm−1): w(OH) 3520br, w(CꢁO)
A benzene solution (20 ml) containing 1 (190 mg,
0.20 mmol) and 2-methyl-2-propen-1-ol (288 mg, 4.0
mmol) was stirred at room temperature for 120 h. The
reaction mixture was concentrated under a reduced
pressure. Addition of hexane to the mixture solidified
the complex. The resulting yellow precipitates were
washed with hexane and dried under a reduced pressure
1
1890vs, w(C–OH) 1090s. H-NMR (CDCl3, −30°C): l
0.35 (d, J=5.1 Hz, 3H, CH3), 1.41 (br, 1H, CH), 1.52
(br, 1H, RuCHaHb), 1.62 (br, 1H, RuCHaHb), 1.82 (br,
1H, CHcHdO), 3.16 (br, 1H, CHcHdO), 7.05–7.34 (m,
30H, Ph). 31P{lH}-NMR (CDCl3, −30°C): l 34.8 (d,
J=332.1 Hz), 42.6 (d, J=332.1 Hz).

K. Hiraki et al. / Journal of Organometallic Chemistry 574 (1999) 121–132
129
3.2. Reaction of 1 with 2-methyl-2-propen-1-ol in
3.3. Reaction of 1 with aldehydes in the presence of
the presence of water
water
A benzene solution (20 ml) involving 1 (477 mg, 0.50
mmol) and 2-methyl-2propen-1-ol (360 mg, 5.0 mmol)
as purchased was refluxed for 48 h. The reaction mix-
ture was concentrated under a reduced pressure and
diluted with hexane to afford yellow precipitates, a
A benzene solution (20 ml) involving 1 (190 mg, 0.20
mmol) and 2-methylpropanal (as purchased, 144 mg,
2.0 mmol) was refluxed for 48 h. The reaction mixture
was treated with a similar work-up as the case of
2-methyl-2-propen-1-ol to precipitate a yellow powdery
mixture of 3a and 3b in a ratio of 6:1 (140 mg, 92%).
A mixture of 1 (160 mg, 0.17 mmol) and cyclohex-
anecarbaldehyde (as purchased, 44 mg, 0.40 mmol) in
benzene (6 ml) was sealed in a glass reaction tube and
heated at 80°C. After heating for 48 h, the reaction
mixture was concentrated under a reduced pressure and
applied to NMR analysis. The 31P{1H}-NMR spectra
of the reaction mixture revealed the formation of the
isomers of the carboxylato complex, [RuCl(p2-
C6H11CO2)(CO)(PPh3)2] (4) (38% yield based on 31P-
NMR). 31P{1H}-NMR (CDCl3) for 4a (trans-form): l
33.9 (s), 4b (cis-form): l 45.4 (d, J=24.4 Hz), 46.1 (d,
J=24.4 Hz). The GLPC analysis of the reaction mix-
ture revealed the formation of cyclohexylmethanol.
In a similar manner, a mixture of 1 (94 mg, 0.10
mmol) and benzaldehyde (as purchased, 24 mg, 0.22
mmol) in benzene (6.5 ml) was allowed to react in a
sealed tube. The NMR analysis showed that [RuCl(p2-
C6H5CO2)(CO)(PPh3)2] (5) was produced (12% yield
based on 31P-NMR). 31P{1H}-NMR (CDCl3) for 5a
mixture
of
the
isomers
of
[RuCl{p2-
(CH3)2CHCO2}(CO)(PPh3)2] (3) (320 mg, 67%). The
precipitates were applied to silica-gel column chro-
matography. The first fraction was eluted with benzene
to give the P,P%-trans isomer 3a. Anal. Found: C, 63.39;
H, 4.94. Calc. for C41H37ClO3P2Ru: C, 63.44; H, 4.80%.
M.p. 252–255°C (dec.). IR (cm−1): w(CꢁO) 1948vs.
1H-NMR (CDCl3): l 0.07 (d, J=6.6 Hz, 6H, CH3),
1.05 (sep. J=6.6 Hz, 1H, CH), 7.38 (t, J=7.3 Hz,
12H, m-Ph), 7.42 (t, J=7.3 Hz, 6H, p-Ph), 7.52 (q,
J=7.3 Hz, 12H, o-Ph). 13C{1H}-NMR (CDC13): l
17.0 (s, CH3), 35.4 (s, CH), 128.1 (br, m-Ph), 130.1 (s,
p-Ph), 130.7 (t, J=25.3 Hz, ipso-Ph), 134.8 (s, o-Ph),
191.8 (s, CO2), 205.4 (t, J=14.6 Hz, CꢁO). 31P{1H}-
NMR (CDCl3): l 33.9 (s).
The second fraction was eluted with chloroform to
afford the P,P%-cis- form 3b. Anal. Found: C, 57.81; H,
4.37. Calc. for C41H37ClO3P2Ru·CHCl3: C, 56.33; H,
4.27. Calc. for C41H37ClO3P2Ru·0.8CHCl3: C, 57.59; H,
4.37%. M.p. 248–251°C (dec.). IR (cm−1): w(CꢁO)
1
1950vs. H-NMR (CDCl3): l 0.63 (d, J=7.3 Hz, 3H,
(trans-form): l 34.3 (s), 5b (cis-form): l 45.0 (d, JPP
24.4 Hz), 46.9 (d, J=24.4 Hz).
=
CH3), 0.75 (d, J=7.3 Hz, 3H, CH3), 1.79 (sep. J=7.3
Hz, 1H, CH), 7.00 (t, J=7.7 Hz, 6H, p-Ph), 7.12 (td,
J=7.7 and 2.2 Hz, 6H, m-Ph), 7.22 (td, J=7.7 and 2.2
Hz, 6H, m-Ph), 7.33 (t, J=7.7 Hz, 6H, o-Ph), 7.40 (t,
J=7.7 Hz, 6H, o-Ph). 13C{1H}-NMR (CDCl3): l 0.1
(s, CH3), 1.1 (s, CH3), 18.9 (s, CH), 128.0–134.9 (m,
Ph), 191.8 (s, CO2), 205.5 (t, J=12.7 Hz, CꢁO).
31P{1H}-NMR (CDCl3): l 45.3 (d, J=24.4 Hz), 46.4
(d, J=24.4 Hz).
Furthermore, 1 (160 mg, 0.17 mmol) reacted simi-
larly with 3-phenylpropanal (as purchased, 50 mg, 0.37
mmol) in benzene (6 ml) to give [RuCl(p2-
C6H5CH2CH2CO2)(CO)(PPh3)2] (6) (42% yield based
on 31P-NMR). 31P{1H}-NMR (CDCl3) for 6a (trans-
form): l 34.8 (s), 6b (cis-form): l 45.4 (d, J=24.4 Hz),
46.2 (d, J=24.4 Hz).
Scheme 3. A plausible mechanism for the formation of 7 and 8.

130
K. Hiraki et al. / Journal of Organometallic Chemistry 574 (1999) 121–132
Table 4
Crystal data for 7 and 8
3.4. Reaction of 1 with 2-methyl-2-propen-1-ol at high
temperature
7
8
A mixture of 1 (602 mg, 0.63 mmol) and dried
2-methyl-2-propen-1-ol (10 ml) was heated at 80°C for
48 h. The reaction mixture was concentrated under a
reduced pressure and applied to silica-gel column chro-
matography. The first fraction was eluted with hexane–
diethyl ether (1:2) to afford pale yellow solids of
[Ru{CH2ꢀC(CH3)CHꢀO}(CO)(PPh3)2] (7) (312 mg,
68%). Anal. Found: C, 67.66; H, 5.13. Calc. for
C41H36O2P2Ru: C, 68.04; H, 5.01%. M.p. 191–193°C
(dec.). IR (cm−1): w(CꢁO) 1915vs. 1H-NMR (CDCl3): l
1.18 (m, 1H, CHaHb), 1.50 (m, 1H, CHaHb), 1.99 (d,
J=2.9 Hz, 3H, CH3), 5.81 (d, J=4.4 Hz, 1H, CH).
13C{1H}-NMR (CDCl3): l 17.4 (s, CH3), 39.7 (d, J=
31.3 Hz, CH2), 99.6 (s, CCH3), 123.8 (s, CHO), 207.6
(t, J=11.7 Hz, CꢁO). 31P{1H}-NMR (CDCl3): l 31.0
(d, J=2.1 Hz), 40.7 (d, J=2.1 Hz).
Formula
C41H36O2P2Ru
723.75
C22H24ClOP
370.86
Formula weight (M)
Color and habit
Crystal size (mm)
Crystal system
Space group
Pale yellow prism
0.40×0.20×0.50
Monoclinic
Cc (No.9)
19.080(2)
10.396(2)
18.994(2)
10.442(8)
3530.3(8)
4
1.362
1488.00
5.69
0.31, 0.028
1.59
Colorless prism
0.40×0.20×0.50
Monoclinic
P21/c (No.14)
11.564(3)
10.032(7)
17.586(2)
106.61(1)
1954(1)
˚
a (A)
˚
b (A)
˚
c (A)
i (°)
V (A )
3
˚
Z
4
Dcalc (g cm−3
F(000)
)
1.260
784.00
2.84
0.050, 0.036
1.59
v(Mo–Kh) (cm−1
R, Rw
)
Goodness-of-Fit
The second fraction was eluted with chloroform–
methanol (4:1) to give [Ph3PCH2CH(CH3)CH2OH]Cl
(8) (112 mg, 48%). Anal. Found: C, 70.53; H, 6.46.
Calc. for C22H24ClOP: C, 71.25; H, 6.52%. M.p. 233–
235°C. IR (cm−1): w(OH) 3275br, w(P–C) 1462vs,
respectively. Tables of hydrogen atom coordinates, an-
isotropic displacement parameters and complete lists of
bond lengths and angles have been deposited at the
Cambridge Crystallographic Data Centre. The intensity
data were collected at 20°C on a Rigaku AFC7S auto-
matic four-circle diffractometer with graphite-
monochromated Mo–Kh radiation. Cell constants were
obtained from the least-squares refinement of the set-
ting angles of the carefully centered reflections (16
reflections in the range 35.87°52q539.42° for 7, and
25 in the range 22.69°52q 536.04° for 8). Azimuthal
scans of several reflections indicated no need for an
absorption correction. The data were corrected for
Lorentz and polarization effects. During the data col-
lection, the intensities of three representative reflections
were measured after every 150 reflections; no variation
was observed.
1
w(C6H5) 1440s, w(C–OH) 1113s. H-NMR (CDCl3): l
0.52 (d, J=6.6 Hz, 3H, CH3), 2.17 (m, 1H, CH), 2.66
(ddd, J=16.0, 9.5 and 12.0 Hz, 1H, PCHaHb), 3.66 (dt,
J=11.4 and 4.6 Hz, 1H, CHcHdO), 3.59 (dd, J=11.4
and 9.0Hz, 1H, CHcHdO),4.94(t, J=16.0 Hz, 1H,
PCHaHb). 13C{1H}-NMR (CDCl3): l 17.6 (s, CH3),
26.1 (d, J=50.9 Hz, PCH2), 32.0 (s, CH), 66.8 (d,
J=11.8 Hz, CH2O), 119.3 (d, J=86.1 Hz, ipso-Ph),
130.5 (d, J=11.8 Hz, m-Ph), 133.7 (d, J=11.8 Hz,
o-Ph), 135.0 (s, p-Ph). 31P{1H}-NMR (CDCl3): l 21.2
(s).
3.4.1. The NMR analysis of the time-programmed
experiment
A mixture of 1 (308 mg) and dried 2-methyl-2-
propen-1-ol (10 ml) was allowed to react in a Schlenk
tube sealed with a rubber septum. After being kept at
room temperature for 72 h, a small part of the reaction
mixture was sampled through the septum with a sy-
ringe. Before the sample was applied to the NMR
measurement, it was concentrated under a reduced
pressure and successively diluted with CDCl3. The rest
of the reaction mixture was allowed to react for addi-
tional 48 h at 50°C before the second sampling. The
last sample was taken after extra 70 h at 65°C.
As for 7, of the 4406 reflections which were collected,
4277 were unique. The structure was solved by heavy-
atom Patterson methods [28] and expanded using
Fourier techniques [29]. The non-hydrogen atoms were
refined anisotropically; the hydrogen atoms were in-
cluded but not refined. The final cycle of full-matrix
least-squares refinement was based on 3572 observed
reflections {I\3|(I)} and 423 variable parameters; the
function minimized was ꢀ w( ꢁ Fo ꢁ−ꢁFc ꢁ )2, where
w
−1=|2(Fo)+[(0.010/2)Fo]2.
As for 8, of the 4966 reflections which were collected,
4740 were unique. The structure was solved by direct
methods [30] and expanded using Fourier techniques
[29]. Thc non-hydrogen atoms were refined anisotropi-
cally; the hydrogen atom coordinates were refined but
their isotropic thermal parameters were held fixed. The
final cycle of full-matrix least-squares refinement was
based on 1730 observed reflections {I\3|(I)} and 299
3.5. Single crystal X-ray structure analysis
Crystal data and details of the measurement for 7
and 8 are summarized in Table 4. The final atomic
coordinates with the equivalent isotropic thermal
parameters for 7 and 8 are reported in Tables 5 and 6,

K. Hiraki et al. / Journal of Organometallic Chemistry 574 (1999) 121–132
131
Table 6
variable parameters; the function minimized was
ꢀ w( ꢁ Fo ꢁ−ꢁFc ꢁ )2, where w−1=|2(Fo)+[(0.010/2)Fo]2.
Neutral atom scattering factors, corrected for
anomalous dispersion, were taken from a literature [31].
All calculations were performed on a Rigaku RASA-7
automatic structure analysis system using the teXsan
crystallographic software package [32].
2
˚
Atomic coordinates and equivalent isotropic thermal parameters (A )
for 8
Atom
x
y
z
Beq
Cl(1)
P(1)
O(1)
C(1)
C(2)
0.8838(2)
0.2706(1)
0.2688(3)
0.1824(4)
0.2296(5)
0.2060(5)
0.1705(6)
0.1849(4)
0.1700(5)
0.1053(5)
0.0591(5)
0.0733(5)
0.1356(5)
0.3070(4)
0.2151(4)
0.2408(5)
0.3580(6)
0.4501(5)
0.4254(4)
0.4079(4)
0.4753(5)
0.5795(5)
0.6162(5)
0.5516(5)
0.4458(4)
0.1457(2)
0.1836(1)
0.8363(1)
0.03744(8)
0.0565(2)
0.0026(3)
5.16(4)
2.96(3)
5.1(1)
3.1(1)
3.5(1)
4.9(2)
5.2(2)
2.8(1)
4.0(2)
4.6(2)
4.5(2)
4.5(2)
3.9(1)
3.0(1)
4.3(1)
4.6(2)
4.8(2)
4.8(2)
4.0(1)
3.0(1)
4.6(2)
4.8(2)
4.3(2)
4.1(2)
3.7(1)
−0.2395(3)
0.0366(5)
−0.0656(5)
−0.2064(6)
−0.0437(7)
0.2904(5)
0.4244(6)
0.5022(6)
0.4478(6)
0.3145(6)
0.2355(5)
0.2699(5)
0.3239(6)
0.3940(6)
0.4071(6)
0.3537(6)
0.2850(5)
0.1455(5)
0.2501(6)
0.2207(6)
0.0985(7)
−0.0057(6)
0.0160(6)
−0.0471(3)
−0.0236(4)
−0.1349(4)
0.0823(3)
C(3)
C(4)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
0.0659(3)
0.1047(4)
0.1610(4)
0.1789(3)
Table 5
2
˚
Atomic coordinates and equivalent isotropic thermal parameters (A )
for 7
0.1385(3)
Atom
x
y
z
Beq
−0.0417(3)
−0.1034(3)
−0.1634(3)
−0.1644(3)
−0.1047(4)
−0.0436(3)
0.1134(3)
Ru(1)
P(1)
P(2)
O(1)
O(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(10) −0.0523(3)
C(11) −0.0600(3)
C(12) −0.1236(4)
C(13) −0.1786(4)
C(14) −0.1708(4)
C(15) −0.1078(3)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(40) −0.1117(3)
C(41) −0.1774(4)
C(42) −0.1806(4)
C(43) −0.1192(5)
C(44) −0.0545(4)
C(45) −0.0502(3)
C(50) −0.1936(3)
C(51) −0.2594(3)
C(52) −0.3258(3)
C(53) −0.3268(4)
C(54) −0.2619(4)
C(55) −0.1961(3)
C(60) −0.1159(3)
C(61) −0.1424(3)
C(62) −0.1440(4)
C(63) −0.1188(4)
C(64) −0.0921(5)
C(65) −0.0912(4)
0.0025
0.02717(7)
0.10481(3)
0.2167(1)
0.2082(1)
0.2555(4)
0.0607(4)
0.2018(5)
−0.0010
0.11340(7)
−0.08456(8)
0.0373(3)
0.0422(2)
−0.0238(3)
0.0553(3)
−0.0067(4)
−0.0775(4)
0.0077(4)
0.1437(3)
0.1790(3)
0.1976(4)
0.1813(5)
0.1467(5)
0.1280(4)
0.1279(3)
0.1983(3)
0.2089(4)
0.1485(5)
0.0800(5)
0.0670(4)
0.1910(3)
0.1937(3)
0.2467(3)
0.2947(4)
2.797(7)
2.87(3)
3.02(3)
6.6(1)
4.0(1)
4.0(1)
3.7(1)
3.9(1)
4.3(2)
5.7(2)
3.4(1)
4.9(2)
6.6(2)
7.0(2)
6.6(2)
4.6(1)
3.1(1)
4.4(1)
5.7(2)
5.9(2)
5.6(2)
4.4(1)
3.0(1)
3.8(1)
4.6(1)
5.5(2)
5.3(2)
4.2(1)
3.6(1)
5.0(2)
6.3(2)
6.6(2)
6.9(2)
5.4(2)
3.3(1)
3.8(1)
4.9(2)
6.0(2)
6.4(2)
5.0(1)
3.4(1)
4.1(1)
5.3(2)
6.2(2)
5.9(2)
4.6(1)
−0.10441(8)
0.1183(3)
−0.0386(2)
0.0718(3)
0.0334(4)
0.0583(3)
0.024(4)
0.1548(4)
0.2151(4)
0.2344(3)
0.1940(3)
−0.0785(5)
−0.0790(5)
−0.0531(6)
−0.0895(6)
0.2453(5)
0.3596(6)
0.3785(7)
0.2862(7)
0.1755(6)
0.1544(5)
0.3744(4)
0.4158(5)
0.5415(6)
0.6216(6)
0.5832(7)
0.4585(5)
0.1231(4)
0.1110(5)
0.0320(6)
−0.0385(6)
−0.0297(6)
0.0525(5)
0.2015(5)
0.1720(6)
0.1688(7)
0.1966(7)
0.2266(8)
0.2274(7)
0.1407(4)
0.2113(5)
0.1564(6)
0.0324(7)
−0.0413(6)
0.0143(5)
0.3811(4)
0.4206(5)
0.5500(6)
0.6415(5)
0.6037(6)
0.4739(5)
0.1409(3)
0.1330(3)
Acknowledgements
This work was financially supported by a Grant-in-
Aid for Scientific Research on Priority Area of Reactive
Organometallics, No. 06227255 from the Ministry of
Education, Science, Sports, and Culture, Japan and
also supported in part (HK) by Itoh Science
Foundation.
0.0731(3)
0.1187(3)
0.1462(3)
0.1305(3)
0.0877(5)
0.0570(3)
0.0914(3)
0.1655(3)
0.2156(3)
0.1921(4)
0.1197(4)
0.0692(3)
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0.2927(3)
0.2404(3)
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