Synthesis and reactivity of complexes 2a-c, their involvement as catalyst precursors for regioselective allylic substitution reactions and related [Ru(Cp*)Cl(Ph2POMe)(RCHCHCH2)] [PF6] η3-allyl ruthenium(IV)inter

Article abstract of DOI:10.1002/ejic.200501051

The synthesis of the new complexes [Ru(Cp*)(L)(MeCN) ₂]-[PF₆] (L = Ph₂POMe or Ph₂P-o- tolyl) and {Ru(Cp*)-[Ph₂PCH₂C(tBu)=O](MeCN)}[PF ₆] (2a-c) is achieved starting from [Ru(Cp*)

Full text of DOI:10.1002/ejic.200501051

FULL PAPER
DOI: 10.1002/ejic.200501051
Synthesis and Reactivity of [Ru(Cp*)(L)(MeCN)2][PF6] (L = Ph2POMe or
Ph2P-o-tolyl) and {Ru(Cp*)[Ph2PCH2C(tBu)=O](MeCN)}[PF6] Complexes,
Their Involvement as Catalyst Precursors for Regioselective Allylic Substitution
Reactions and Related [Ru(Cp*)Cl(Ph2POMe)(RCHCHCH2)][PF6] η3-Allyl
Ruthenium(IV) Intermediates
Bernard Demerseman,*[a] Jean-Luc Renaud,[a] Loïc Toupet,[a] Claudie Hubert,[a] and
Christian Bruneau[a]
Keywords: Allyl ligands / Allylation / Homogeneous catalysis / Regioselectivity / Ruthenium
The synthesis of the new complexes [Ru(Cp*)(L)(MeCN)2]-
[PF6] (L Ph2POMe or Ph2P-o-tolyl) and {Ru(Cp*)-
[PF6] and [Ru(Cp*)Cl(Ph2POMe)(RCHCHCH2)][PF6] (R =
=
Me; nPr, 8d; or Ph, 8e) are obtained by reacting 2a with the
appropriate allylic halide. The X-ray crystal structure deter-
mination of the compounds 8d and 8e disclosed an endo-
trans-RCHCHCH2 η3-allyl ligand. The formation of branched
allyl aryl ethers is regioselectively favoured when complexes
2a–c are involved as catalyst precursors for the etherification
of cinnamyl chloride, chlorohexene and 3-chloro-4-phen-
ylbut-1-ene with phenol, p-methoxyphenol, cresols and (o or
p)-chlorophenols, in the presence of K2CO3.
[Ph2PCH2C(tBu)=O](MeCN)}[PF6] (2a–c) is achieved starting
from [Ru(Cp*)(MeCN)3][PF6]. The acetonitrile ligands in
complexes 2a–c are labile, as emphasised by the easy forma-
tion of {Ru(Cp*)(CO)2[Ph2PCH2C(=O)tBu]}[PF6] (3). The
keto-phosphane is used as a tool to convert 3 into {Ru(Cp*)-
(CO)[Ph2PCH2C(tBu)=O]}[PF6] (5). Complex 5 reacts with
1,1-diphenyl-2-propyn-1-ol in methanol as solvent to
afford the vinyl-carbene complex {Ru(Cp*)(CO)[=C(OMe)-
CH=CPh2][Ph2PCH2C(=O)tBu]}[PF6]. The new η3-allyl ruthe-
nium(IV) derivatives [Ru(Cp*)Cl(Ph2POMe)(CH2CMeCH2)]-
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
stereoisomerism arising from the presence of four distinct
coordinating centres besides the cyclopentadienyl ligand.[6]
Introduction
Recently,
the
labile
ruthenium()
complex
[Ru(Cp*)(MeCN)3][PF6] (1) (Cp* = pentamethylcyclopen-
tadienyl) was disclosed as an efficient catalyst precursor for
the allylation of phenols with cinnamyl derivatives accord-
ing to stereospecific and regioselective processes.[1,2]
Furthermore, enantioselective synthesis was also achieved
in the additional presence of a chiral bis-oxazoline ligand.[3]
Enantioselective allylic amination and alkylation involving
related catalysts based on tethered CpЈ rings resulting in
planar chirality at the ruthenium centre have also been re-
ported.[4] From a mechanistic point of view, these catalytic
reactions occur through transient formation of electrophilic
η3-allyl ruthenium() species.[5] Indeed, complexes
[Ru(Cp*)X(MeCN)(η3-RCHCHCH2)][PF6] resulted from
the oxidative addition of allylic halides to 1, but have been
disclosed to be a mixture of stereoisomers in solution, as
enantiomeric pairs (see Scheme 1).[2] The recently reported
tethered complexes [Ru(CpЈ-PR2)Cl(η3-CH2CRCH2)][PF6]
involved a symmetrical η3-allyl ligand precluding analogous
Scheme 1. Stereoisomerism and isomerism from unsymmetrical η3-
CH2CHCHR allyl ligand.
Therefore, no information was available concerning the
relationship between the regioselectivity of the catalytic nu-
cleophilic substitution and the stereoselective formation of
the putative η3-allyl ruthenium() intermediate. Moreover,
using such ruthenium catalysts, the regioselective formation
of branched products by nucleophilic attack at an unsym-
metrical η3-RCHCHCH2 allyl ligand, as depicted in
Scheme 1, largely remained a challenge when R was an
alkyl group instead of an aryl one arising from cinnamyl
substrates. On the other hand, while the reactivity of
[a] Institut de Chimie de Rennes, UMR-CNRS 6509, Organomé-
talliques et Catalyse, Université de Rennes 1,
35042 Rennes Cedex, France
Fax: +33-223236939
E-mail: bernard.demerseman@univ-rennes1.fr
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B. Demerseman, J.-L. Renaud, L. Toupet, C. Hubert, C. Bruneau
FULL PAPER
[Ru(Cp)(PR3)(MeCN)2][PF6] complexes towards alkynes structure determination easily formed according to dif-
continued to stimulate studies,[7] little was known concern- fusion of diethyl ether into a concentrated dichloromethane
ing their reactivity towards allylic organic substrates, al- solution. An ORTEP drawing of 2a is shown in Figure 1
though [Ru(Cp)Br(PR3)(η3-CH2CHCH2)][PF6] complexes and selected bond lengths and angles are given in the cap-
have been synthesised.[8]
tion.
We wish to report herein (i) the reaction between
[Ru(Cp*)(MeCN)3][PF6] and methyl diphenylphosphinite,
o-tolyldiphenylphosphane or a hemilabile β-keto-phos-
phane, which provides an efficient tool for the building of
new organometallic derivatives, (ii) the synthesis of
[Ru(Cp*)X(Ph2POMe)(RCHCHCH2)][PF6] η3-allyl ruthe-
nium() complexes bearing an unsymmetrical monosubsti-
tuted allyl ligand and (iii) the involvement of these com-
plexes as catalyst precursors for regioselective allylic etheri-
fication.
Results and Discussion
Synthesis of Complexes
With a procedure very similar to the reported synthesis
of [Ru(Cp*)(PEt3)(MeCN)2][PF6],[9] the reaction of
[Ru(Cp*)(MeCN)3][PF6] (1) with one equiv. of methyl di-
phenylphosphinite or of the bulkier o-tolyldiphenylphos-
phane selectively resulted in the substitution of one aceto-
nitrile ligand to afford the expected complexes
[Ru(Cp*)(L)(MeCN)2][PF6] (L = Ph2POMe, 2a and L =
Ph2P-o-tolyl, 2b), in 78% and 99% yield, respectively
(Scheme 2).
Figure 1. ORTEP drawing of 2a showing 50% probability thermal
ellipsoids. The PF6 anion is omitted for clarity. Selected bond
lengths [Å] and angles [°]: Ru1–N1 2.076(2), Ru1–N2 2.067(2),
Ru1–P1 2.2894(6); N1–Ru1–N2 87.74(8), N1–Ru1–P1 94.55(6),
N2–Ru1–P1 90.77(6).
The cation of 2a showed the expected piano-stool geome-
try. The N–Ru–N and N–Ru–P angles are close to 90° and
the structure of 2a thus consisted of a pseudo-octahedron
with the Cp* ligand occupying three facial coordination
sites.
Complex 2c retained two labile coordinating atoms, as
indicated by its reaction with carbon monoxide, which oc-
curred under mild conditions (1 atm, ambient temperature)
to straightforwardly afford the dicarbonyl complex 3
(Scheme 3).
The formal selective substitution of the acetonitrile li-
gand in 2c by carbon monoxide was indirectly achieved by
reacting 3 with Me3NO·2H2O to form the enolato-phos-
phane derivative 4 (Scheme 3). The reaction consisted of
Scheme 2. Synthesis of the new complexes 2a–c.
Distinctly, the reaction between 1 and the β-keto-phos- the oxidation of one carbon monoxide ligand into carbon
phane Ph2PCH2C(=O)tBu showed the substitution of two dioxide, thus also generating NMe3, which subsequently de-
acetonitrile ligands to afford 2c wherein the functional protonated the keto-phosphane. The neutral complex 4 was
phosphane acted as a chelate, in 95% yield (Scheme 2). The then easily reprotonated with HPF6 as its aqueous solution
new complexes 2a–c were characterised by 1H, 13C{1H}, or with HBF4 as its Me2O adduct, to obtain 5 and 5Ј,
13C DEPT and 31P{1H} NMR, IR spectroscopy and ele- respectively, in yields up to 81%. The protonation of 4 was
1
mental analysis. The H and 31P{1H} NMR spectra of 2a– also achieved with hydrochloric acid, but the additional co-
c unambiguously indicated the presence of coordinated ace- ordination of the chloride anion resulted in the neutral
tonitrile and one phosphorus ligand besides the Cp* one. chloro complex 6 (Scheme 3). These reactions emphasised
Additionally, IR spectroscopy provided evidence for the co- the usefulness of hemilabile keto-phosphanes as a tool for
ordination of the keto function in 2c (ν = 1611 cm–1) as the building of coordination compounds. Furthermore, the
˜
previously specified in the case of CpRu complexes.[10] coordinated keto-function in 5 is labile enough to allow the
Attempts of recrystallisation of 2b,c invariably led to oils coordination of alkynols such as 1,1-diphenyl-2-propyn-1-
that transform to yellow solids under prolonged vacuum. ol. Using methanol as solvent, the reaction led at room tem-
By contrast, orange crystals of 2a suitable for X-ray crystal perature to a red precipitate of the vinyl-carbene derivative
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Synthesis and Reactivity of Ruthenium Complexes and Related Intermediates
FULL PAPER
tion of complexes 8 was observed to be sluggish in acetoni-
trile as solvent. Thus, the addition of cinnamyl chloride (an
excess) to a solution of 2a in acetonitrile showed only about
10% of 2a to be converted into 8e after standing for two
days at room temperature, as monitored by 1H and 31P{1H}
NMR spectroscopy. Indicating an irreversible formation,
solutions of 8e in acetonitrile were observed to be stable
and unchanged after 8 days. Such an observation of a for-
mation hindered by the presence of acetonitrile as coordi-
nating solvent suggests a dissociative mechanism. The coor-
dination of the olefinic bond of the allylic halide at a tran-
sient 16e-intermediate resulting from the loss of an acetoni-
trile ligand by 2a would be a preliminary step allowing sub-
sequent intramolecular oxidative addition.
Scheme 3. Reactivity of complex 2c: (i) CO,
1 atm; (ii)
Me3NO·2H2O; (iii) HPF6 or HBF4; (iv) HCl; (v) Ph2C(OH)
CϵCH, MeOH.
7 (Scheme 3). The reaction might be conceived as an ad-
dition of methanol to a transient allenylidene species as pre-
viously investigated for [Ru(Cp)(CO)(acetone)(PiPr3)]-
[BF4].[11] Complexes 3–7 were characterised from a combi-
1
nation of H, 13C{1H}, 13C DEPT and 31P{1H} NMR, IR
spectroscopy and elemental analysis. Owing to the chiral
ruthenium centre, the two PCH2 protons of the keto-phos-
Scheme 4. Synthesis of the new η3-allyl ruthenium() complexes,
phane were found to be diastereotopic in complexes 2c, 5, 8a–e.
5Ј, 6 and 7. Characteristic of the vinyl-carbene ligand in 7
is the observation by 13C{1H} NMR spectroscopy of a very
Complexes 8a–e were characterised by NMR spectro-
2
low field resonance at δ = 303.7 ppm (d, JPC = 2.5 Hz) scopic techniques including 1H{31P} for 8c,d, and elemental
corresponding to the Ru=C carbon nucleus.[11] Some steric analysis. Of main interest, CD2Cl2 solutions of 8a–e dis-
congestion in 7 is likely responsible for the broadness of closed single species by H, 13C{1H} and 31P{1H} NMR
1
both the 31P{1H} NMR resonance at δ = 38.8 ppm and the spectroscopy. The characterisation of complexes 8a–e was
1H NMR resonance assigned to the OMe protons at δ = finally completed by an X-ray crystal structure determi-
4.05 ppm. IR spectroscopic data accounted for the presence nation of 8d and 8e. ORTEP drawings of cations of 8d and
of carbon monoxide as a ligand and for the coordination 8e are shown on Figure 2 and Figure 3, respectively. Se-
mode of the functional phosphane (ν Ϸ 1700 cm–1, uncoor- lected bond lengths and angles are given in the captions of
˜
dinated C=O, in 3, 6 and 7; ν Ϸ 1600 cm–1, coordinated the figures.
˜
C=O, in 5 and 5Ј; ν = 1500 cm–1, C=CO, in 4).[10]
Cations of 8d and 8e displayed a square-pyramidal struc-
˜
Complexes 2a–c were observed to react with allylic ha- ture with a chlorine, a phosphorus and the terminal carbon
lides but crystallisable products were obtained only starting atoms of an endo-η3-allyl ligand, at basal positions. Likely
from 2a. Using dichloromethane as solvent, the η3-allyl ru- resulting from an increased steric demand, the Ru–P bond
thenium() derivatives 8a–e resulted from the reaction at length in 8d or 8e [Ru1–P1 = 2.368(1) and 2.360(1) Å,
room temperature between 2a and 3-chloro-2-methylpro- respectively] is longer than in 2a [Ru1–P1 = 2.2894(6) Å].
pene, crotyl chloride or bromide, chlorohexene as a mixture Moreover, the phosphorus atom in 8d and 8e is located in
of isomeric nPrCH=CHCH2Cl and nPrCH(Cl)CH=CH2, a trans position relative to the substituted allylic carbon and
and cinnamyl chloride (Scheme 4). Complexes 8a–e were such an arrangement would minimise steric constraints be-
isolated in high yield (62–85%) as yellow to red crystals tween the allyl and the phosphorus ligands. The Ru–Cl
that were observed to be stable in air. Of interest, the forma- bond lengths [2.406(1) Å in 8d, 2.396(1) Å in 8e] revealed
Eur. J. Inorg. Chem. 2006, 1371–1380
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FULL PAPER
C13 bond length involving the substituted terminal carbon
of the η3-allyl ligand was significantly longer, especially in
the case of 8e [2.452(4) vs. 2.339(4) Å in 8d]. These observa-
tions are in agreement with those arising from the study of
the complexes [Ru(Cp*)(phenanthroline)(η3-cinnamyl)]-
[PF6]2,[12]
[Ru(Cp*)Cl(MeCN)(η3-cinnamyl)][PF6].[13]
minor contribution from
formal η2-olefinic
[Ru(Cp*)Br(MeCN)(η3-crotyl)][PF6][2]
and
A
a
CH2=CH–C(+)HR coordination of the allyl ligand might
intuitively account for both observation of a longer Ru–
CHR bond and enhanced electrophilic reactivity at the sub-
stituted allylic carbon.[2,12,13] The comparison between the
Ru–CHR bond lengths in 8d and 8e [2.339(4) and
2.452(4) Å, respectively] obviously suggested a reduced con-
tribution from the formal η2-olefinic coordination of the
allyl ligand in 8d. Therefore, high regioselectivities in favour
of branched products might be expected to be more difficult
to reach when starting from unsymmetrical alkyl-allylic
substrates compared to cinnamyl derivatives.[2] However,
the location of a bulky phosphane ligand close to the un-
substituted terminal allylic carbon atom, as displayed in 8d
and 8e, might distinctly contribute to favour nucleophilic
addition at the substituted one. To test these assumptions,
the study of the potential of complexes 2a–c as catalyst pre-
cursors for ruthenium-catalysed allylic substitution reac-
tions was undertaken.
Figure 2. ORTEP drawing of 8d showing 50% probability thermal
ellipsoids. The PF6 anion is omitted for clarity. Selected bond
lengths [Å] and angles [°]: Ru1–C11 2.191(4), Ru1–C12 2.198(4),
Ru1–C13 2.339(4), Ru1–P1 2.368(1), C11–C12 1.406(6), C12–C13
1.395(6), C13–C14 1.497(6), Ru1–P1 2.368(1); C11–C12–C13
119.1(4), C12–C13–C14 123.7(4).
Allylation Reactions Catalysed by Complexes 2a–c
The characterisation of an η3-allyl ruthenium() com-
plex arising from an oxidative addition reaction between
[Ru(Cp*)(MeCN)3][PF6] and tert-butyl cinnamyl carbonate
recently provided further evidence for the key role of η3-
allyl ruthenium() catalytic intermediates in ruthenium-ca-
talysed nucleophilic allylic substitution reactions.[14] The ac-
tivity of complexes 2a–c as catalyst precursors for the al-
lylation of dimethyl sodiomalonate with methyl cinnamyl
carbonate was investigated. Thus, the addition of dimethyl
sodiomalonate (1.2 equiv.) to a solution of methyl cinnamyl
carbonate (0.5 mmol) in THF (3.0 mL) in the presence of
2a–c (1.5 mol-%) at ambient temperature led to the mono-
substituted dimethyl malonate 9 as a mixture of branched
(B) and linear (L) isomers [Equation (1)], and disclosed a
favoured formation of the branched isomer (Table 1).
Figure 3. ORTEP drawing of 8e showing 50% probability thermal
ellipsoids. The PF6 anion is omitted for clarity. Selected bond
lengths [Å] and angles [°]: Ru1–C11 2.182(5), Ru1–C12 2.210(4),
Ru1–C13 2.452(4), C11–C12 1.398(6), C12–C13 1.396(6), C13–C14
1.457(6), Ru1–P1 2.360(1); C11–C12–C13 119.5(4), C12–C13–C14
125.7(4).
no special feature and are very close to the values pre-
viously reported in the case of the related complexes
[Ru(Cp*)Cl(MeCN)(η3-PhCHCHCH2)][PF6] and [Ru(Cp*)
Cl2(η3-PhCHCHCH2)] [2.3998(7) and 2.398(3) Å, respec-
tively].[5,13]
The only difference between 8d and 8e was an alkyl n-
propyl group instead of a phenyl group, respectively, as the
substituent linked to one terminal carbon of the η3-allyl
(1)
The results given in Table 1 clearly indicate that the three
ligand. The Ru–C bond lengths involving the unsubstituted catalyst precursors 2a–c provided complete conversion after
terminal allylic C11 carbon atom [2.191(4) Å in 8d and 16 h of reaction. The regioselectivities in favour of the
2.182(5) Å in 8e] and the medium C12 carbon atom branched isomer of 9, B/L ranging between 86:14 with 2c
[2.198(4) Å in 8d and 2.210(4) Å in 8e] were close. The Ru– and 92:8 with 2a, were fairly good in comparison with those
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Synthesis and Reactivity of Ruthenium Complexes and Related Intermediates
FULL PAPER
Table 1. Comparison of complexes 2a–c as catalyst precursors for nitrile or THF, thus hindering the preliminary η2-olefinic
the allylation of dimethyl sodiomalonate with methyl cinnamyl car-
coordination of cinnamyl chloride as required for catalytic
activity. The catalytic process proceeded smoothly for the
bonate.[a]
Entry
Catalyst
Conversion[b][c] B/L ratio
allylation of various phenols in dichloromethane as solvent.
Good regioselectivities were obtained starting from p-meth-
oxyphenol (entry 4) and cresols (entries 5–7) as substituted
phenols. Chlorophenols were also involved in the catalytic
process (entries 8, 9) but only o-chlorophenol provided
good regioselectivity.
Allyl aryl ethers arising from cinnamyl derivatives, valu-
able intermediates in organic chemistry, have drawn the
main interest,[15] but another challenge is the development
of efficient access to branched allyl aryl ethers starting from
aliphatic allylic halides (vs. cinnamyl chloride-type sub-
strates). The allylation of phenols with selected aliphatic or
unconjugated allylic halides in the presence of 2a–c as cata-
lyst precursors was then investigated. Chlorohexene, synthe-
sised as a 4:1 mixture of linear nPrCH=CHCH2Cl and
branched nPrCH(Cl)CH=CH2 isomers starting from trans-
2-hexen-1-ol and PCl3,[16] reacted with various phenols to
afford the allyl aryl ethers 11a–g, as mixtures of branched
nPrCH(OAr)CH=CH2 and linear nPrCH=CHCH2OAr iso-
mers [Equation (3)]. The results are given in Table 3.
1
2
3
2a
2b
2c
100
100
100
92:8
90:10
86:14
[a] Conditions: 0.6 mmol of dimethyl sodiomalonate, 0.5 mmol of
methyl cinnamyl carbonate, 0.0075 mmol of 2a in 3 mL of THF,
room temperature, 16 h. [b] Relative to methyl cinnamyl carbonate
1
(%). [c] As determined by H NMR spectroscopy.
observed using 1 as the catalyst precursor.[1] However, com-
plexes 2a–c, as well as 1,[2] were unable to catalyse this al-
lylic alkylation without prior deprotonation of dimethyl
malonate as achieved with [RuCp*(bipy)(CH3CN)][PF6]
precursors.[12]
The reaction of phenol with cinnamyl chloride in the
presence of 2a and potassium carbonate in dichlorometh-
ane as solvent was investigated also [Equation (2)]. The re-
sults are given in Table 2. Under experimental conditions
analogous to those used with 1 as catalyst,[2] the reaction
led to the formation of the allyl phenyl ether 10a in a 85:15
branched to linear ratio (entry 1).
(3)
(2)
Table 3. Allylation of phenols ArOH with chlorohexene in the pres-
Table 2. Allylation of phenols ArOH with PhCH=CHCH2Cl in the
ence of 2a–c.[a]
presence of 2a.[a]
Entry Cata-
lyst
Ar
Conver-
sion[b][c]
Prod-
ucts
B/L ra-
tio
Entry
Ar
Conversion[b][c] Products
B/L ratio
85:15
1
Ph
Ph
Ph
100
0
10a
1
2a
2a
2a
2b
2c
2a
Ph
Ph
Ph
Ph
100
100
100
94
100
100
11a
11a
11a
11a
11a
11b
75:25
75:25
57:43
77:23
70:30
61:39
2[d]
3[e]
4
2[d]
3[e]
4
0
p-MeOC6H4 76
o-tolyl
m-tolyl
p-tolyl
o-ClC6H4
p-ClC6H4
10b
10c
10d
10e
10f
10g
92:8
5
6
7
8
43
75
61
52
100
88:12
73:27
88:12
86:14
50:50
5
6
Ph
p-Me-
OC6H4
o-tolyl
m-tolyl
p-tolyl
o-ClC6H4
p-ClC6H4
7
8
9
10
11
2a
2a
2a
2a
2a
74
62
88
62
99
11c
11d
11e
11f
11g
81:19
75:25
75:25
84:16
49:51
9
[a] Conditions: 1.2 mmol of ArOH, 1.2 mmol of K2CO3, 1.0 mmol
of cinnamyl chloride, 0.015 mmol of 2a in 6 mL of CH2Cl2, room
temperature, 16 h. [b] Relative to cinnamyl chloride (%). [c] As de-
termined by H NMR spectroscopy. [d] THF as solvent. [e] Aceto-
nitrile as solvent.
1
[a] Conditions: 1.2 mmol of ArOH, 1.5 mmol of K2CO3, 1.0 mmol
of chlorohexene, 0.015 mmol of 2a–c in 6 mL of THF, room tem-
perature, 16 h. [b] Relative to chlorohexene (%). [c] As determined
by 1H NMR spectroscopy. [d] Dichloromethane as solvent. [e] Ace-
tonitrile as solvent.
The regioselectivity was still fairly good although lower
than that obtained with complex 1.[2] Moreover, attempts
to use THF or acetonitrile as solvent disclosed a lack of
reactivity (entries 2, 3), whereas acetonitrile provided the
In a typical run, the addition of phenol (1.2 equiv.) to
best results in the case of catalyst 1.[2] These observations chlorohexene (1.0 mmol) and K2CO3 (1.5 equiv.) in THF
suggested that the entrance of a phosphane ligand in com- (6.0 mL) in the presence of 2a (1.5 mol-%) for 16 h at ambi-
plexes 2 would result in the strongest coordination of aceto- ent temperature resulted in the complete consumption of
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FULL PAPER
chlorohexene and led to the formation of the allyl phenyl poor B/L = 1.5:1 regioselectivity,[2] significantly increased
ether 11a in a 75:25 B/L ratio (entry 1). Using complex 1 regioselectivities up to B/L = 92:8 (entries 1, 2) were
under similar catalytic conditions, chlorohexene was also reached when catalyst 2a was used. THF was an appropri-
converted into 11a, but the regioselectivity was moderate, ate solvent but much lower conversion and regioselectivity
as emphasised by a B/L ratio of 60:40 in acetonitrile and were obtained in dichloromethane or acetonitrile (entries 1–
70:30 in acetone as solvent.[2] In the presence of complexes 3). It is worth noting the lack of reactivity when (o- or p-)
2a–c, the regioselectivity was slightly improved using THF chlorophenols were involved as the nucleophile (entries 8,
or dichloromethane as solvent (entries 1, 2). As observed 9), whereas good regioselectivities up to B/L = 96:4 were
when starting from cinnamyl chloride, acetonitrile markedly reached when p-methoxyphenol or (o-, m- or p-)cresols were
disfavoured regioselectivity (entry 3). The involvement of 2b involved as the nucleophile (entries 4–7).
and 2c as catalysts (entries 4, 5) resulted in regioselectivities
located in the same range as from 2a. Complex 2a was se-
Conclusions
lected for the allylation of the substituted phenols. Using
THF as solvent, satisfactory conversion and regioselectivity
were reached with p-methoxyphenol and cresols (entries 6–
9). The involvement of p-chlorophenol led to a 1:1 mixture
of the branched and linear isomers of 11g (entry 11), while
o-chlorophenol was less reactive but provided a good B/L
= 84:16 regioselectivity (entry 10). The low selectivity ob-
served with p-chlorophenol might result from enhanced
competition of the noncatalysed process, which contributed
to the consumption of allylic halide but selectively led to
the linear ether.
Readily available from benzyl bromide and allyl chlo-
ride,[17] 3-chloro-4-phenylbut-1-ene, PhCH2CH(Cl)CH=
CH2, offered both the convenience of low volatility facilita-
ting experimental work and an opportunity to test a pure
branched allylic chloride under such catalytic conditions
[Equation (4)]. The results are given in Table 4.
The reaction of one equiv. of phosphorus ligand with
[Ru(Cp*)(MeCN)3][PF6] (1) allowed the selective substitu-
tion of one acetonitrile ligand, and the involvement of a
hemilabile β-keto-phosphane provided a tool to selectively
achieve the successive substitution of the three acetonitrile
ligands by one phosphane, one carbon monoxide and one
vinyl-carbene ligand. The products retaining acetonitrile as
a ligand reacted with allylic halides to afford η3-allyl ruthe-
nium() complexes and behave as catalyst precursors for
allylic etherification of phenols with allylic chlorides in the
presence of K2CO3, and alkylation of cinnamyl carbonate
with dimethyl sodiomalonate under mild conditions. Al-
though slightly less reactive than the unsubstituted parent
complex 1, the phosphane derivatives also favoured the for-
mation of branched products when an unsymmetrical mon-
osubstituted allylic substrate was involved, especially when
starting from alkyl-substituted allylic substrates such as
chlorohexene and 3-chloro-4-phenylbut-1-ene.
Experimental Section
General Comments: The reactions were performed under inert ar-
gon according to Schlenk-type techniques. THF, diethyl ether and
dichloromethane were distilled after drying according to conven-
tional methods, whereas HPLC grade acetonitrile was straightfor-
wardly used. NMR spectra were recorded at 297 K with AC 200
FT and AC 300 Bruker instruments and referenced internally to
the solvent peak. IR spectra were recorded as Nujol mulls with
Bruker IFS28. Elemental analyses were performed by the “Service
de Microanalyse du CNRS” Vernaison, France. Complex 1 was
synthesised according to the reported procedure.[2] Commercially
available allylic halides were used without further purification
whereas chlorohexene and 3-chloro-4-phenylbut-1-ene were pre-
pared according to procedures described in the literature.[16,17]
(4)
Table 4. Allylation of phenols ArOH with PhCH2CH(Cl)CH=CH2
catalysed by 2a.[a]
Entry Ar
Conver-
sion[b][c]
Products
B/L ratio
1
Ph
Ph
Ph
87
60
34
12a
12a
12a
12b
12c
12d
12e
92:8
73: 7
50:50
96:4
92:8
96:4
91:9
2[d]
3[e]
4
p-MeOC6H4 88
5
6
o-tolyl
m-tolyl
89
100
93
0
[Ru(Cp*)(Ph2POMe)(MeCN)2][PF6] (2a): Methyl diphenylphos-
phinite (2.0 mL, 9.98 mmol) was added to a cold solution (–80 °C)
of 1 (5.04 g, 10.0 mmol) in a mixture of dichloromethane (70 mL)
and acetonitrile (20 mL). After being stirred overnight at room
temperature, the mixture was evaporated under vacuum. The crude
product was dissolved in dichloromethane (80 mL) and the orange
solution was covered with diethyl ether (200 mL). The natural dif-
fusion of solvents resulted in the formation of orange crystals of
7
8
9
p-tolyl
o-ClC6H4
p-ClC6H4
0
[a] Conditions: 1.2 mmol of ArOH, 1.2 mmol of K2CO3, 1.0 mmol
of allylic chloride, 0.015 mmol of 2a–c in 6 mL of THF, room tem-
perature, 16 h. [b] Relative to allylic chloride (%). [c] As determined
by 1H NMR spectroscopy. [d] Dichloromethane as solvent. [e] Ace-
tonitrile as solvent.
1
2a. Yield: 5.30 g, 78%. H NMR (200.13 MHz, CD2Cl2): δ = 1.57
4
5
(d, JPH = 2.0 Hz, 15 H, C5Me5), 2.27 (d, JPH = 1.3 Hz, 6 H,
3
Whereas the allylation of phenoxide anion in the pres-
MeCN), 3.45 (d, JPH = 12.4 Hz, 3 H, OMe), 7.48–7.57 (m, 10 H,
ence of 3 mol-% of 1 afforded the ether 12a with a rather Ph) ppm. 13C{1H} NMR (50.32 MHz, CD2Cl2): δ = 4.2 (s, MeCN),
1376
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 1371–1380

Synthesis and Reactivity of Ruthenium Complexes and Related Intermediates
FULL PAPER
9.5 (s, C5Me5), 53.5 (d, 2J = 5.7 Hz, OMe), 89.0 (d, 2J = 2.2 Hz,
CD2Cl2): δ = 0.97 (s, 9 H, tBu), 1.72 (d, JPH = 2.0 Hz, 15 H,
4
2
2
C5Me5), 126.4 (s, MeCN), 128.7 (d, J = 9.3 Hz, Ph, ortho), 130.8
C5Me5), 3.83 (d, JPH = 9.6 Hz, 2 H, PCH2), 7.33–7.56 (m, 10 H,
4
3
(d, J = 2.4 Hz, Ph, para), 131.8 (d, J = 12.4 Hz, Ph, meta), 137.1
(d, 1J = 37.3 Hz, Ph, ipso) ppm. 31P{1H} NMR (81.01 MHz,
CD2Cl2): δ = 143.7 (s). C27H34F6N2OP2Ru (679.59): calcd. C 47.72,
H 5.04, N 4.12, P 9.12; found C 47.56, H 5.12, N 4.06, P 9.17.
Ph) ppm. 13C{1H} NMR (50.32 MHz, CD2Cl2): δ = 9.8 (s, C5Me5),
1
3
26.2 (s, CMe3), 40.0 (d, J = 36.8 Hz, PCH2), 45.8 (d, J = 2.2 Hz,
CMe3), 103.6 (s, C5Me5), 130.0 (d, 1J = 50.2 Hz, Ph, ipso), 130.0
(d, 2J = 11.1 Hz, Ph, ortho), 132.5 (d, 3J = 11.6 Hz, Ph, meta),
132.6 (d, 4J = 3.0 Hz, Ph, para), 198.8 (d, 2J = 15.6 Hz, CϵO),
209.7 (d, 2J = 4.0 Hz, C=O) ppm. 31P{1H} NMR (121.50 MHz,
CD2Cl2): δ = 32.5 (s) ppm. C30H36F6O3P2Ru·CH2Cl2 (806.56):
calcd. C 46.16, H 4.75, Cl 8.79, P 7.68; found C 46.47, H 4.68, Cl
7.35, P 7.67 (some presence of the minor form free of dichloro-
methane is likely responsible for the high carbon and low chlorine
values).
[Ru(Cp*)(Ph2P-o-tolyl)(MeCN)2][PF6] (2b): Complex 2b was simi-
larly obtained by adding o-tolyldiphenylphosphane (1.68 g,
6.07 mmol) to a cold solution of 1 (3.06 g, 6.07 mmol) in a mixture
of dichloromethane (70 mL) and acetonitrile (20 mL). After being
stirred overnight at room temperature, the mixture was evaporated
under vacuum to leave an oil that slowly crystallised. Diethyl ether
(30 mL) was then added and the mixture was stirred to obtain a
yellow powder that was collected by filtration and dried under vac-
uum. Yield: 4.45 g, 99%. 1H NMR (200.13 MHz, CD2Cl2): δ =
Ru(Cp*)(CO)[Ph2PCH=C(tBu)O] (4): A mixture consisting of 3
(6.25 g, 7.75 mmol), Me3NO·2H2O (1.00 g, 9.00 mmol) and meth-
anol (60 mL) was stirred overnight to afford a yellow slurry. Dissol-
ution of the precipitate was subsequently obtained upon heating
and completed by adding some dichloromethane (Ϸ10 mL). The
hot solution deposited yellow crystals of 4 upon cooling to –20 °C
after partial removal of solvents (20 mL) under a stream of argon.
Yield: 3.43 g, 81%. Note that further concentration of the solution
led to a mixture of additional 4 and of ammonium salt. However,
treatment of the mother liquor with an excess of NH4Cl allowed
conversion of residual 4 into 6, which may be subsequently sepa-
4
1.42 (d, JPH = 1.6 Hz, 15 H, C5Me5), 2.11 (s, 3 H, Me), 2.20 (d,
5JPH = 1.5 Hz, 6 H, MeCN), 7.05–7.51 (m, 14 H, Ph) ppm.
13C{1H} NMR (50.32 MHz, CD2Cl2): δ = 4.2 (s, MeCN), 9.2 (s,
3
2
C5Me5), 22.5 (d, J = 7.0 Hz, Me), 87.1 (d, J = 2.3 Hz, C5Me5),
126.4 (s, MeCN), 125.9–142.8 (m, C6 rings) ppm. 31P{1H} NMR
(81.01 MHz, CD2Cl2): δ = 46.2 (s) ppm. C33H38F6N2P2Ru (739.69):
calcd. C 53.59, H 5.18, N 3.79, P 8.37; found C 52.98, H 5.22, N
3.71, P 8.33.
{Ru(Cp*)[Ph2PCH2C(tBu)=O](MeCN)}[PF6] (2c): A solution of
Ph2PCH2C(=O)tBu (2.58 g, 9.07 mmol) in dichloromethane
(20 mL) was added to a cold solution (–80 °C) of 1 (4.58 g,
9.08 mmol) in a mixture of dichloromethane (60 mL) and acetoni-
trile (10 mL). After being stirred overnight at room temperature,
the mixture was evaporated under vacuum. Methanol (30 mL) and
diethyl ether (40 mL) were added to the residue and the mixture
was stirred while an orange precipitate formed. The mixture was
evaporated, then methanol (8 mL) and diethyl ether (60 mL) were
added. The resulting orange crystalline precipitate was collected by
rated according to selective dissolution in diethyl ether. IR: ν =
˜
1933 cm–1, CϵO; 1500 cm–1, C=CO. 1H NMR (300.13 MHz,
4
CD2Cl2): δ = 1.19 (s, 9 H, tBu), 1.53 (d, JPH = 1.5 Hz, 15 H,
2
C5Me5), 4.59 (d, JPH = 2.9 Hz, 1 H, PCH=), 7.13–7.66 (m, 10 H,
Ph) ppm. 13C{1H} NMR (50.32 MHz, CD2Cl2): δ = 9.7 (s, C5Me5),
30.0 (s, CMe3), 38.5 (d, 3J = 12.2 Hz, CMe3), 74.5 (d, 1J = 59.8 Hz,
PCH), 95.3 (s, C5Me5), 128.2 (d, 2J = 10.3 Hz, Ph, ortho), 128.4 (d,
4
2J = 11.0 Hz, Ph, ortho), 128.9 (d, J = 2.4 Hz, Ph, para), 129.8 (s,
3
3
para), 131.7 (d, J = 9.8 Hz, Ph, meta), 133.3 (d, J = 11.0 Hz, Ph,
meta), 138.5 (d, 1J = 59.8 Hz, Ph, ipso), 140.2 (d, 1J = 40.3 Hz, Ph,
2
2
filtration, then washed with diethyl ether and dried under vacuum.
ipso), 200.8 (d, J = 17.1 Hz, =CO), 206.0 (d, J = 19.5 Hz, CϵO)
ppm. 13C NMR (50.32 MHz, CD2Cl2, selected values): δ = 74.5
(dd, JHC = 162.4, JPC = 58.6 Hz, PCH=) ppm. 31P{1H} NMR
(121.50 MHz, CD2Cl2): δ = 55.3 (s) ppm. C29H35O2PRu (547.64):
calcd. C 63.60, H 6.44, P 5.66; found C 63.65, H 6.39, P 5.98.
1
Yield: 6.06 g, 95%. IR: ν = 2269 cm–1, CϵN; 1611 cm–1, C=O. H
˜
4
NMR (300.13 MHz, CD2Cl2): δ = 1.26 (s, 9 H, tBu), 1.47 (d, JPH
= 1.8 Hz, 15 H, C5Me5), 2.09 (d, 5JPH = 1.5 Hz, 3 H, MeCN), 2.94
2
2
2
(dd, JHH = 18.6, JPH = 7.5 Hz, 1 H, PCH2, Ha), 4.24 (dd, JHH
2
= 18.6, JPH = 10.1 Hz, 1 H, PCH2, Hb), 6.85–7.65 (m, 10 H, Ph)
{Ru(Cp*)(CO)[Ph2PCH2C(tBu)=O]}[PF6] (5): A commercial 60%
weight aqueous solution of HPF6 (0.54 mL, 3.66 mmol) was added
to a cold slurry (–80 °C) of 4 (2.00 g, 3.65 mmol) in methanol
(40 mL). The mixture was warmed to room temperature and fur-
ther stirred for 1 h. The resulting yellow solution was evaporated
to dryness under vacuum and the residue was dissolved in dichloro-
methane (20 mL). The solution was covered with methanol (5 mL)
then diethyl ether (140 mL) to afford orange needles. Yield: 2.05 g,
ppm. 13C{1H} NMR (50.32 MHz, CD2Cl2): δ = 4.1 (s, MeCN), 9.9
(s, C5Me5), 27.0 (s, CMe3), 45.8 (d, 3J = 1.8 Hz, CMe3), 46.5 (d, 1J
2
= 21.5 Hz, PCH2), 85.7 (d, J = 2.2 Hz, C5Me5), 127.7 (s, MeCN),
129.2 (d, 2J = 10.3 Hz, Ph, ortho), 129.4 (d, 1J = 42.1 Hz, Ph, ipso),
129.6 (d, 2J = 10.2 Hz, Ph, ortho), 130.7 (d, 3J = 10.9 Hz, Ph, meta),
4
4
130.7 (d, J = 2.5 Hz, Ph, para), 132.1 (d, J = 1.3 Hz, Ph, para),
134.9 (d, 3J = 14.0 Hz, Ph, meta), 137.0 (d, 1J = 39.3 Hz, Ph, ipso),
228.9 (d, 2J = 7.1 Hz, C=O) ppm. 31P{1H} NMR (121.50 MHz,
CD2Cl2): δ = 62.1 (s) ppm. C30H39F6NOP2Ru (706.65): calcd. C
50.99, H 5.56, N 1.98, P 8.77; found C 50.37, H 5.64, N 1.89, P
8.79.
81%. IR: ν = 1975 cm–1, CϵO; 1603 cm–1, C=O. 1H NMR
˜
4
(200.13 MHz, CD2Cl2): δ = 1.38 (s, 9 H, tBu), 1.70 (d, JPH
2.0 Hz, 15 H, C5Me5), 3.33 (dd, JHH = 18.5, JPH = 8.6 Hz, 1 H,
=
2
2
2
2
PCH2, Ha), 4.77 (dd, JHH = 18.4, JPH = 10.7 Hz, 1 H, PCH2,
Hb), 6.79–6.89 (m, 2 H, Ph), 7.48–7.72 (m, 8 H, Ph) ppm. 13C{1H}
NMR (50.32 MHz, CD2Cl2): δ = 9.9 (s, C5Me5), 27.1 (s, CMe3),
{Ru(Cp*)(CO)2[Ph2PCH2C(=O)tBu]}[PF6]·CH2Cl2 (3): A solution
of 2c (6.06 g, 8.58 mmol) in a mixture of methanol (40 mL) and
dichloromethane (40 mL) was stirred for 24 h under carbon mono-
xide and was then evaporated under vacuum. The residue was dis-
solved in dichloromethane (25 mL) and the solution was covered
with methanol (5 mL) then diethyl ether (250 mL), to afford pale
brown crystals. Yield: 6.03 g, 87%. Note that several recrystalli-
46.8 (d, J = 2.3 Hz, CMe3), 48.8 (d, 1J = 29.2 Hz, PCH2), 97.6 (d,
3
2J = 1.6 Hz, C5Me5), 128.9 (d, J = 57.1 Hz, Ph, ipso), 129.9 (d, J
1
2
2
= 10.2 Hz, Ph, ortho), 130.1 (d, J = 11.7 Hz, Ph, ortho), 130.4 (d,
3J = 11.0 Hz, Ph, meta), 132.1 (d, 4J = 2.5 Hz, Ph, para), 132.6
(part of d, Ph, ipso), 133.3 (d, 4J = 2.5 Hz, Ph, para and hidden
part of d, Ph, ipso), 134.5 (d, 3J = 12.5 Hz, Ph, meta), 202.8 (d, 2J =
1
sations are needed to obtain almost colourless crystals. H NMR
2
spectroscopy and elemental analysis provided evidence for the re-
tention of one molecule of dichloromethane. However, a minor
16.5 Hz, CϵO), 233.1 (d, J = 4.0 Hz, C=O) ppm. 31P{1H} NMR
(81.01 MHz, CD2Cl2): δ = 66.5 (s), –143.2 (sept, PF6) ppm.
C29H36F6O2P2Ru (693.61): calcd. C 50.22, H 5.23, P 8.93; found C
50.06, H 5.31, P 8.47.
crystalline form free of dichloromethane was also detected. IR: ν
˜
= 2046, 2005 cm–1, CϵO; 1701 cm–1, C=O. 1H NMR (300.13 MHz,
Eur. J. Inorg. Chem. 2006, 1371–1380
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1377

B. Demerseman, J.-L. Renaud, L. Toupet, C. Hubert, C. Bruneau
FULL PAPER
{Ru(Cp*)(CO)[Ph2PCH2C(tBu)=O]}[BF4] (5Ј): Large yellow-brown
crystals of 5Ј were similarly obtained in 80% yield after adding
HBF4·OMe2 (as a 0.7  solution in methanol) to a cold slurry of 4
[Ru(Cp*)Cl(Ph2POMe)(CH2CMeCH2)][PF6] (8a): An excess of 3-
chloro-2-methylpropene (0.40 mL, 4.1 mmol) was added to a solu-
tion of 2a (0.67 g, 0.99 mmol) in dichloromethane (25 mL). After
being stirred overnight, the solution was covered with diethyl ether
in methanol. IR: ν = 1957 cm–1, CϵO; 1597 cm–1, C=O. 1H NMR
˜
4
1
(200.13 MHz, CD2Cl2): δ = 1.38 (s, 9 H, tBu), 1.70 (d, JPH
2.0 Hz, 15 H, C5Me5), 3.38 (dd, JHH = 18.7, JPH = 8.6 Hz, 1 H, NMR (200.13 MHz, CD2Cl2): δ = 1.01 (s, 3 H, Me), 1.71 (d, JPH
=
(100 mL) to afford orange-yellow crystals. Yield: 0.48 g, 70%. H
2
2
4
2
2
PCH2, Ha), 4.85 (dd, JHH = 18.6, JPH = 10.7 Hz, 1 H, PCH2,
= 2.2 Hz, 15 H, C5Me5), 2.01 (broad s, 1 H, CH2, anti), 3.07 (d,
Hb), 6.79–7.72 (m, 10 H, Ph) ppm. 13C{1H} NMR (50.32 MHz,
3JPH = 3.8 Hz, 1 H, CH2, anti), 3.41 (dd, JHH Ϸ JPH Ϸ 2.3 Hz,
4
3
3
3
CD2Cl2): δ = 9.9 (s, C5Me5), 27.1 (s, CMe3), 46.8 (d, J = 2.4 Hz,
1 H, CH2, syn), 3.60 (broad d, JPH = 11.0 Hz, 1 H, CH2, syn),
CMe3), 48.7 (d, 1J = 29.0 Hz, PCH2), 97.5 (d, 2J = 1.5 Hz, C5Me5),
129.0 (d, 1J = 57.2 Hz, Ph, ipso), 129.8 (d, 2J = 10.0 Hz, Ph, ortho),
3.79 (d, JPH = 11.0 Hz, 3 H, OMe), 7.45–7.70 (m, 10 H, Ph) ppm.
3
13C{1H} NMR (50.32 MHz, CD2Cl2): δ = 9.9 (s, C5Me5), 17.0 (s,
130.0 (d, 2J = 10.4 Hz, Ph, ortho), 130.4 (d, 3J = 10.9 Hz, Ph, meta), Me, allyl), 53.4 (d, 2J = 4.0 Hz, CH2), 58.5 (d, 2J = 14.8 Hz, OMe),
4
1
132.0 (d, J = 2.2 Hz, Ph, para), 133.0 (d, J = 39.8 Hz, Ph, ipso),
133.2 (d, J = 3.0 Hz, Ph, para), 134.6 (d, J = 12.7 Hz, Ph, meta),
70.2 (d, 2J = 6.2 Hz, CH2), 107.2 (d, 2J = 1.5 Hz, C5Me5), 116.1
(d, 2J = 1.6 Hz, CMe, allyl), 128.5 (d, 2J = 10.1 Hz, Ph, ortho),
128.6 (d, 1J = 43.6 Hz, Ph, ipso), 129.4 (d, 2J = 10.3 Hz, Ph, ortho),
4
3
2
2
202.9 (d, J = 17.3 Hz, CϵO), 233.4 (d, J = 4.9 Hz, C=O) ppm.
31P{1H} NMR (81.01 MHz, CD2Cl2):
δ
=
66.2 (s) ppm.
131.9 (d, J = 43.1 Hz, Ph, ipso), 133.2 (d, J = 9.2 Hz, Ph, meta),
1
3
4
4
C29H36BF4O2PRu (635.45): calcd. C 54.81, H 5.71, P 4.87; found
C 54.79, H 5.76, P 4.87.
133.2 (d, J = 3.8 Hz, Ph, para), 133.3 (d, J = 2.5 Hz, Ph, para),
135.7 (d, 3J = 11.0 Hz, Ph, meta) ppm. 31P{1H} NMR (81.01 MHz,
CD2Cl2): δ = 124.5 (s) ppm. C27H35ClF6OP2Ru (688.04): calcd. C
47.13, H 5.13, Cl 5.15, P 9.00; found C 47.11, H 5.02, Cl 5.27, P
8.70.
Ru(Cp*)Cl(CO)[Ph2PCH2C(=O)tBu] (6): 37% weight aqueous hy-
drochloric acid (0.30 mL, 3.65 mmol) was added to a cold slurry
(–80 °C) of 4 (2.00 g, 3.65 mmol) in methanol (35 mL). The mixture
was warmed to room temperature and further stirred for 1 h. The
resulting solution was evaporated to dryness under vacuum and the
residue was extracted with diethyl ether (30 mL). The solution was
filtered and then slowly evaporated under vacuum to leave an
[Ru(Cp*)Cl(Ph2POMe)(MeCHCHCH2)][PF6] (8b): An excess of 3-
chloro-1-butene (0.50 mL, 5.0 mmol) was added to a solution of 2a
(0.84 g, 1.24 mmol) in dichloromethane (25 mL). After being
stirred for 1 h, the solution was covered with diethyl ether (110 mL)
to afford orange-yellow crystals. Yield: 0.72 g, 84%. 1H NMR
orange-yellow solid. Yield: 2.04 g, 96%. IR: ν = 1916 cm–1, CϵO;
˜
1690 cm–1, C=O. 1H NMR (200.13 MHz, CDCl3): δ = 0.82 (s, 9 H,
(200.13 MHz, CD2Cl2): δ = 1.27 (dd, JHH = 6.3, JPH = 1.4 Hz, 3
3
4
4
2
4
tBu), 1.48 (d, JPH = 1.9 Hz, 15 H, C5Me5), 3.90 (dd, JHH = 16.1,
H, Me), 1.79 (d, JPH = 2.2 Hz, 15.5 H, C5Me5 and part of d, 0.5
2JPH = 6.6 Hz, 1 H, PCH2, Ha), 4.08 (dd, JHH = 16.0, JPH
=
H, CH2, anti), 1.83 (part of d, 0.5 H, CH2, anti), 3.29 (dddd,
2
2
3
3
8.5 Hz, 1 H, PCH2, Hb), 7.39–7.43 (m, 6 H, Ph), 7.65–7.78 (m, 4
3JHHtrans Ϸ 10.4, JHHcis = 6.0, JPH = 3.9 Hz, 1 H, CH), 3.67 (d,
H, Ph) ppm. 1H NMR (200.13 MHz, CD2Cl2): δ = 0.86 (s, 9 H, 3JPH = 11.0 Hz, 3 H, OMe), 3.72–3.83 (m, 2 H, CHMe and CH2,
tBu), 1.49 (d, 4JPH = 1.8 Hz, 15 H, C5Me5), 4.00 (d, 2JPH = 7.8 Hz,
syn), 7.41–7.71 (m, 10 H, Ph) ppm. 13C{1H} NMR (50.32 MHz,
2 H, PCH2), 7.43–7.77 (m, 10 H, Ph) ppm. 13C{1H} NMR CD2Cl2): δ = 9.4 (s, C5Me5), 16.9 (d, J = 1.5 Hz, CHMe), 52.8 (d,
3
(50.32 MHz, CD2Cl2): δ = 9.9 (s, C5Me5), 26.5 (s, CMe3), 38.0 (d,
2J = 3.9 Hz, CH2), 58.1 (d, 2J = 14.7 Hz, OMe), 96.4 (d, 2J Ϸ 3 Hz,
1J = 23.4 Hz, PCH2), 46.2 (d, 3J = 1.5 Hz, CMe3), 96.9 (d, 2J =
CHMe) 96.4 (s, CH), 106.0 (d, J = 1.6 Hz, C5Me5), 125.8 (d, J =
2
1
2
2
2
2
2.5 Hz, C5Me5), 128.6 (d, J = 10.2 Hz, Ph, ortho), 128.8 (d, J =
49.4 Hz, Ph, ipso), 127.9 (d, J = 10.9 Hz, Ph, ortho), 128.7 (d, J
= 10.4 Hz, Ph, ortho), 130.2 (d, J = 44.5 Hz, Ph, ipso), 131.2 (d,
4
1
9.3 Hz, Ph, ortho), 130.9 (d, J = 1.6 Hz, 2 C, Ph, para), 133.3 (d,
1J = 40.0 Hz, Ph, ipso), 134.2 (d, 3J = 11.0 Hz, Ph, meta), 134.3 (d, 3J = 9.2 Hz, Ph, meta), 132.2 (d, J = 3.0 Hz, Ph, para), 132.9 (d,
4
3J = 10.2 Hz, Ph, meta), 134.3 (d, 1J = 46.9 Hz, Ph, ipso), 207.2 (d, 4J = 2.5 Hz, Ph, para), 135.8 (d, 3J = 10.3 Hz, Ph, meta) ppm.
2J = 21.2 Hz, CϵO), 210.8 (d, 2J = 7.9 Hz, C=O) ppm. 31P{1H}
NMR (81.01 MHz, CD2Cl2): δ = 41.9 (s) ppm. C29H36ClO2PRu
(584.10): calcd. C 59.63, H 6.21, Cl 6.07, P 5.30; found C 60.09, H
6.38, Cl 6.30, P 5.20.
31P{1H} NMR (81.01 MHz, CD2Cl2):
δ = 128.5 (s) ppm.
C27H35ClF6OP2Ru (688.04): calcd. C 47.13, H 5.13, Cl 5.15, P 9.00;
found C 46.85, H 5.27, Cl 4.97, P 9.20.
[Ru(Cp*)Br(Ph2POMe)(MeCHCHCH2)][PF6] (8c): An excess of
crotyl bromide (0.40 mL, 3.9 mmol) was added to a solution of 2a
(0.86 g, 1.27 mmol) in dichloromethane (25 mL). After being
{Ru(Cp*)(CO)[=C(OMe)CH=CPh2][Ph2PCH2C(=O)tBu]}[PF6]
(7): A solution of 5 (1.00 g, 1.44 mmol) and of 1,1-diphenyl-2-pro-
pyn-1-ol (0.50 g, 2.40 mmol) in methanol (30 mL) was stirred at stirred for 1 h, the solution was covered with diethyl ether (120 mL)
room temperature for 20 h. The resulting dark red precipitate was
collected by filtration and washed with diethyl ether (20 mL), then
dissolved in dichloromethane (25 mL). This solution was covered
first with methanol (10 mL) then diethyl ether (120 mL) to afford
to afford orange crystals. Yield: 0.72 g, 77%. 1H NMR
3
4
(200.13 MHz, CD2Cl2): δ = 1.53 (dd, JHH = 6.1, JPH = 1.5 Hz, 3
3
H, Me), 1.76 (broad d, JHHtrans = 10.0 Hz, 1 H, CH2, anti), 1.87
4
3
(d, JPH = 2.0 Hz, 15 H, C5Me5), 3.21 (dddd, JHHtrans = 11.1 and
orange-red crystals. Yield: 1.16 g, 88%. IR: ν = 1948 cm–1, CϵO;
9.9, 3JHHcis = 5.9, 3JPH = 3.6 Hz, 1 H, CH), 3.59 (d, 3JPH = 11.0 Hz,
3 H, OMe), 3.71 (ddq, JHHtrans = 11.0, JHH = 6.2, JPH = 3.2 Hz,
˜
1
3
3
3
1709 cm–1, C=O. H NMR (200.13 MHz, CD2Cl2): δ = 1.06 (s, 9
4
2
3
2
3
H, tBu), 1.56 (d, JPH = 1.7 Hz, 15 H, C5Me5), 3.76 (dd, JHH
=
1 H, CHMe), 3.85 (ddd, JHHcis = 6.0, JHH = 2.2, JPH = 8.4 Hz,
2
2
2
17.3, JPH = 7.2 Hz, 1 H, PCH2, Ha), 3.86 (dd, JHH = 17.5, JPH
1 H, CH2, syn), 7.38–7.72 (m, 10 H, Ph) ppm. 1H{31P} NMR
= 8.1 Hz, 1 H, PCH2, Hb), 4.05 (s, broad, 3 H, OMe), 6.15 (d, 4JPH
(200.13 MHz, CD2Cl2, selected values): δ = 1.79 (d, JHHtrans
=
=
3
= 1.8 Hz, 1 H, CH=), 6.99–7.59 (m, 20 H, Ph) ppm. 13C{1H} NMR 10.2 Hz, 1 H, CH2, anti), 3.22 (dt, JHHtrans Ϸ 10.5, JHHcis
3
3
3
3
(50.32 MHz, CD2Cl2): δ = 9.8 (s, C5Me5), 26.3 (s, CMe3), 38.9 (d,
6.4 Hz, 1 H, CH), 3.71 (dq, JHHtrans = 11.7, JHH = 6.1 Hz, 1 H,
1J = 31.9 Hz, PCH2), 46.0 (s, CMe3), 65.6 (s, OCH3), 103.0 (s, CHMe), 3.87 (broad d, JHHcis = 4.3 Hz, 1 H, CH2, syn) ppm.
3
C5Me5), 129.0–144.6 (m, CH= and Ph), 205.0 (d, 2J = 17.1 Hz,
13C{1H} NMR (50.32 MHz, CD2Cl2): δ = 10.5 (s, C5Me5), 15.1 (d,
2
2
CϵO), 209.0 (d, J = 6.3 Hz, C=O), 303.7 (d, J = 2.5 Hz, Ru=C)
ppm. 31P{1H} NMR (81.01 MHz, CD2Cl2): δ = 38.8 (s, broad)
ppm. C45H50F6O3P2Ru (915.90): calcd. C 59.01, H 5.50, P 6.76;
found C 58.73, H 5.57, P 6.60.
3J = 1.6 Hz, CHMe), 53.1 (d, 2J = 4.4 Hz, CH2), 58.8 (d, 2J =
2
14.8 Hz, OMe), 96.3 (s, CH), 96.9 (d, J = 4.8 Hz, CHMe), 106.5
(d, 2J = 1.7 Hz, C5Me5), 127.5 (d, 1J = 50.9 Hz, Ph, ipso), 128.6
(d, 2J = 10.3 Hz, Ph, ortho), 129.5 (d, 2J = 10.1 Hz, Ph, ortho),
1378
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Eur. J. Inorg. Chem. 2006, 1371–1380

Synthesis and Reactivity of Ruthenium Complexes and Related Intermediates
FULL PAPER
1
3
4
3
130.8 (d, J = 45.0 Hz, Ph, ipso), 132.1 (d, J = 8.6 Hz, Ph, meta), Ph, para), 133.3 (d, J = 2.3 Hz, Ph, para), 136.2 (d, J = 10.6 Hz,
4
4
133.1 (d, J = 2.1 Hz, Ph, para), 133.8 (d, J = 2.2 Hz, Ph, para),
Ph, meta) ppm. 31P{1H} NMR (81.01 MHz, CD2Cl2): δ = 128.2 (s)
137.0 (d, 3J = 11.1 Hz, Ph, meta) ppm. 31P{1H} NMR (81.01 MHz, ppm. C29H39ClF6OP2Ru (716.09): calcd. C 48.64, H 5.49, Cl 4.95,
CD2Cl2): δ = 128.7 (s) ppm. C27H35BrF6OP2Ru (732.49): calcd. C P 8.65; found C 48.39, H 5.55, Cl 5.16, P 8.72.
44.27, H 4.82, Br 10.91, P 8.46; found C 44.18, H 4.80, Br 10.57,
[Ru(Cp*)Cl(Ph2POMe)(PhCHCHCH2)][PF6] (8e): An excess of
cinnamyl chloride (0.60 mL, 4.3 mmol) was added to a solution of
P 7.96.
[Ru(Cp*)Cl(Ph2POMe)(nPrCHCHCH2)][PF6] (8d): An excess of
2a (1.00 g, 1.47 mmol) in dichloromethane (25 mL). After being
chlorohexene (0.80 mL of a 4:1 mixture of linear 1-chloro-2-hexene
stirred for 20 h, the solution was covered first with methanol
and branched 3-chloro-1-hexene) was added to a solution of 2a
(15 mL), then diethyl ether (130 mL) to afford dark red crystals.
(1.84 g, 2.71 mmol) in dichloromethane (25 mL). After being
1
Yield: 0.68 g, 62%. H NMR (200.13 MHz, CD2Cl2): δ = 1.79 (d,
stirred for 1 h, the solution was covered with diethyl ether (150 mL)
4JPH = 1.9 Hz, 15 H, C5Me5), 2.12 (d, broad, JHH = 9.2 Hz, 1 H,
3
to afford orange-yellow crystals. Yield: 1.65 g, 85%. 1H NMR
3
CH2, anti), 3.71 (d, JPH = 11.0 Hz, 3 H, OMe), 3.79–3.93 (m,
(200.13 MHz, CD2Cl2): δ = 0.92 (m, broad, 3 H, Me), 1.49 (m,
broad, 4 H, 2 CH2), 1.78 (d, JPH = 2.2 Hz, 15 H, C5Me5 and
overlapped: m, 1 H, CH2, anti), 3.32 (m, 1 H, CH), 3.67 (d, JPH
= 10.8 Hz, 3 H, OMe and overlapped: m, 1 H, nPrCH), 3.86 (ddd,
3JHHcis = 5.9, 2JHH = 2.2, 3JPH = 8.2 Hz, 1 H, CH2, syn), 7.42–7.68
(m, 10 H, Ph) ppm. 1H{31P} NMR (200.13 MHz, CD2Cl2): δ =
0.94 (m, broad, 3 H, Me), 1.51 (m, broad, 4 H, 2 CH2), 1.80 (s, 15
H, C5Me5 and overlapped: m, 1 H, CH2, anti), 3.34 (ddd, 3JHHtrans
3
broad, 1 H, CH), 3.94–4.03 (m, 1 H, CH2, syn), 4.73 (dd, JHH
=
4
3
12.0, JPH = 3.1 Hz, 1 H, CHPh), 6.94–7.70 (m, 15 H, Ph) ppm.
13C{1H} NMR (50.32 MHz, CD2Cl2): δ = 10.0 (s, C5Me5), 51.4 (d,
2J = 5.0 Hz, CH2), 58.5 (d, 2J = 14.9 Hz, OMe), 91.0 (s, CH), 103.4
3
2
(d, J = 4.7 Hz, CHPh), 106.3 (s, C5Me5), 127.0 (s, Ph, ipso), 128.4
(s, Ph, ortho), 128.4 (d, 2J = 10.0 Hz, PhP, ortho), 129.3 (d, 2J =
1
10.0 Hz, PhP, ortho), 131.2 (d, J = 44.5 Hz, PhP, ipso), 131.5 (d,
3J = 8.6 Hz, PhP, meta), 131.5 (s, Ph, para), 132.3 (s, Ph, meta),
132.5 (d, 1J = 34.5 Hz, PhP, ipso), 133.0 (d, 4J = 2.6 Hz, PhP, para),
133.4 (d, 4J = 2.3 Hz, PhP, para), 136.0 (d, 3J = 10.3 Hz, PhP, meta)
ppm. 31P{1H} NMR (81.01 MHz, CD2Cl2): δ = 129.0 (s) ppm.
C32H37ClF6OP2Ru (750.11): calcd. C 51.24, H 4.97, Cl 4.73, P 8.26;
found C 51.05, H 5.08, Cl 4.65, P 8.49.
3
3
Ϸ JHЈHtrans Ϸ 10.5, JHHcis = 6.1 Hz,1 H, CH), 3.69 (s, 3 H, OMe
3
2
and overlapped: m, 1 H, nPrCH), 3.88 (dd, JHHcis = 6.1, JHH
=
2.1 Hz, 1 H, CH2, syn), 7.47–7.70 (m, 10 H, Ph) ppm. 13C{1H}
NMR (50.32 MHz, CD2Cl2): δ = 9.9 (s, C5Me5), 14.0 (s, CH3), 23.1
(s, CH2), 33.9 (s, CH2) 53.3 (s, =CH2), 58.5 (d, 2J = 15.0 Hz, OMe),
96.1 (s, CH), 100.4 (d, J = 4.4 Hz, nPrCH), 106.5 (d, 2J = 1.8 Hz,
2
1
2
C5Me5), 126.2 (d, J = 49.1 Hz, Ph, ipso), 128.4 (d, J = 10.7 Hz,
X-ray Crystallography: The samples were studied with a NONIUS
Ph, ortho), 129.2 (d, 2J = 9.9 Hz, Ph, ortho), 130.6 (d, 1J = 45.1 Hz, Kappa CCD (2a, 8d) or Oxford Diffraction Xcalibur Saphir 3 (8e)
3
4
Ph, ipso), 131.6 (d, J = 8.5 Hz, Ph, meta), 132.7 (d, J = 2.6 Hz, diffractometer with graphite monochromator. Crystallographic
Table 5. Crystallographic data for complexes 2a, 8d and 8e.[a]
Complex
2a
8d
8e
Empirical formula
Molecular weight [gmol–1]
Crystal size [mm]
Crystal system
Space group
a [Å]
C27H34F6N2OP2Ru
679.57
0.30×0.30×0.28
monoclinic
P21/c
14.8025(2)
11.5147(1)
17.0685(2)
90.258(1)
2909.23(6)
4
C29H39ClF6OP2Ru
716.06
0.22×0.22×0.22
orthorhombic
Pbca
14.6192(2)
20.5531(2)
C32H37ClF6OP2Ru
750.08
0.24×0.22×0.20
orthorhombic
Pbca
14.8064(6)
21.0835(8)
b [Å]
c [Å]
20.7975(2)
20.6072(9)
β [°]
Volume [Å3]
Z
6248.0(1)
8
1.522
293(2)
2928
6433.0(5)
8
1.549
293(2)
3056
Density [gcm–3]
Temperature [K]
F(000)
1.552
130(1)
1384
Mo-Kα radiation, λ [Å]
Absorption coefficient [mm–1]
θ range [°]
0.71073
0.711
2.39–27.48
0 Ͻ h Ͻ 19
0 Ͻ k Ͻ 14
–22 Ͻ l Ͻ 22
52105
0.71073
0.747
2.21–27.00
0 Ͻ h Ͻ 18
0 Ͻ k Ͻ 26
0 Ͻ l Ͻ 26
105939
0.71073
0.730
3.08–27.00
–12 Ͻ h Ͻ 12
–26 Ͻ k Ͻ 26
–26 Ͻ l Ͻ 26
27593
Index ranges
Reflections collected
Independent reflections
Reflections I Ͼ 2σ(I)
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)]
6652 (Rint = 0.030)
6121
6811 (Rint = 0.050)
5637
5899 (Rint = 0.0519)
4981
Full-matrix least-squares on F2
6811/0/374
1.003
6652/0/371
1.065
R1 = 0.0374
wR2 = 0.0968
R1 = 0.0408
wR2 = 0.1004
1.005 and –0.797
5899/0/389
1.086
R1 = 0.0545
wR2 = 0.1411
R1 = 0.0642
wR2 = 0.1507
0.982 and –0.786
R1 = 0.0492
wR2 = 0.1347
R1 = 0.0612
wR2 = 0.1514
0.709 and –0.734
R indices (all data)
Largest diff. peak/hole [eÅ–3]
[a] w = 1/[σ2(Fo2) + (0.0518P)2 + 6.0599P] (2a), 1/[σ2(Fo2) + (0.0843P)2 + 11.8733P] (8d), 1/[σ2(Fo2) + (0.0754P)2 + 15.1442P] (8e), where
2
2
P = (Fo + 2Fc )/3.
Eur. J. Inorg. Chem. 2006, 1371–1380
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1379

B. Demerseman, J.-L. Renaud, L. Toupet, C. Hubert, C. Bruneau
FULL PAPER
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data are given in Table 5. The cell parameters were obtained with
Denzo and Scalepack[18] (2a, 8d) and data collection with NONIUS
KappaCCD Software[19] (2a, 8d) and CrysAlis RED[20] (8e). Data
reduction was carried out with Denzo and Scalepack[18] (2a, 8d)
and CrysAlis RED[20] (8e). The structures were solved with
SIR−97, which revealed the non-hydrogen atoms.[21] After aniso-
tropic refinement, many hydrogen atoms were found with Fourier
difference calculations. The whole structures were refined with
SHELXL97 by full-matrix least-squares methods on F2 (x, y, z, βij
for Ru, P, N, Cl, F, C and O atoms; x, y, z in riding mode for H
atoms).[22] ORTEP views were prepared with PLATON98.[23]
CCDC-261933 (for 2a), -272359 (for 8d) and -258428 (for 8e) con-
tain the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Catalytic Experiments: Organic compounds were identified from
[15]
[16]
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1
1
the comparison of H NMR spectra with available H NMR spec-
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(0.015 mmol, 1.5 mol-%), K2CO3 (1.2–1.5 equiv.) and solvent
(6.0 mL). The slurry was stirred at room temperature for 16 h and
then was evaporated under vacuum. The residue was extracted with
dichloromethane (20 mL) and the solution was filtered. The filtrate
was evaporated to leave the crude product that was analysed by
1H NMR spectroscopy (CDCl3) for conversion and regioselectivity
determination.
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Received: November 24, 2005
Published Online: February 21, 2006
1380
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 1371–1380