Direct preparation of carbonatoruthenium(II) derivatives (2) (see abstract) and their use as precursor of the ruthenium dihydride (p-cymene) [PCy(3)] and the [Ru(VI)-arene] (L)[(MeCN)(2)] [[BF(4)](2)] complexes

Article abstract of DOI:10.1002/ejic.200500973

[RuCl₂(η⁶-arene)(PR₃)] complexes react with K₂CO₃ in the presence of water to afford the carbonatoruthenium(II) derivatives [Ru(η²-O₂CO) (η⁶-arene)(PR₃)] (2; arene = p-cymene, R = Cy, Ph, or Me; arene = hexamethylbenzene, R = Me) involving a planar Ru(η²- O₂CO) moiety as shown by X-ray crystal structure determination of 2a (p-cymene, PCy₃) and 2d (hexamethylbenzene, PMe₃). The complex [Ru(η²-O₂CO)(p-cymene)(PCy₃)] is cleanly converted in hot methanol into the dihydride (RuH₂(p-cymene) (PCy₃)]. The related complexes [Ru(η²-O ₂CO)(η⁶-arene)(IMes)] [arene = p-cymene or hexamethylbenzene, IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] are straightforwardly prepared by treating [RuCl₂(η⁶- arene)]₂ precursors with 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride and K₂CO₃ in THF at reflux. The removal of the carbonato ligand from complexes 2 with HBF₄ in the presence of acetonitrile leads to the dicationic derivatives [Ru(η⁶-arene)(L) (MeCN)₂][BF₄]₂ (L = PR₃ or IMes). Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Full text of DOI:10.1002/ejic.200500973

FULL PAPER
DOI: 10.1002/ejic.200500973
Direct Preparation of [Ru(η2-O2CO)(η6-arene)(L)] Carbonate Complexes (L =
Phosphane, Carbene) and Their Use as Precursors of [RuH2(p-cymene)(PCy3)]
and [Ru(η6-arene)(L)(MeCN)2][BF4]2: X-ray Crystal Structure Determination
of [Ru(η2-O2CO)(p-cymene)(PCy3)]·1/2CH2Cl2 and [Ru(η2-O2CO)(η6-C6Me6)-
(PMe3)]·H2O
Bernard Demerseman,*[a] Mbaye Diagne Mbaye,[a] David Sémeril,[a] Loïc Toupet,[a]
Christian Bruneau,[a] and Pierre H. Dixneuf[a]
Keywords: Arene ligands / Hydrides / O ligands / Reactive intermediates / Ruthenium
[RuCl2(η6-arene)(PR3)] complexes react with K2CO3 in the
presence of water to afford the carbonatoruthenium(II) deriv- azol-2-ylidene] are straightforwardly prepared by treating
methylbenzene, IMes = 1,3-bis(2,4,6-trimethylphenyl)imid-
atives [Ru(η2-O2CO)(η6-arene)(PR3)] (2; arene = p-cymene, R
= Cy, Ph, or Me; arene = hexamethylbenzene, R = Me) involv-
ing a planar Ru(η2-O2CO) moiety as shown by X-ray crystal
structure determination of 2a (p-cymene, PCy3) and 2d
(hexamethylbenzene, PMe3). The complex [Ru(η2-O2CO)(p-
cymene)(PCy3)] is cleanly converted in hot methanol into the
dihydride [RuH2(p-cymene)(PCy3)]. The related complexes
[Ru(η2-O2CO)(η6-arene)(IMes)] [arene = p-cymene or hexa-
[RuCl2(η6-arene)]2 precursors with 1,3-bis(2,4,6-trimeth-
ylphenyl)imidazolium chloride and K2CO3 in THF at reflux.
The removal of the carbonato ligand from complexes 2 with
HBF4 in the presence of acetonitrile leads to the dicationic
derivatives [Ru(η6-arene)(L)(MeCN)2][BF4]2 (L
= PR3 or
IMes).
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
metal carbonate and a ruthenium halide or cationic ruthe-
nium precursor,[8–11] reaction of carbon dioxide with an oxa-
ruthenacyclobutane,[8] hydrolysis of carbamato ligands,[12]
oxidation of coordinated carbon monoxide,[13–18] and
reactions involving a formal reduction of carbon dioxide
(2 CO2 + 2e– Ǟ CO + CO32–).[19,20] From a structural point
of view, mononuclear carbonatoruthenium() complexes
contain an Ru(η2-O2CO) fragment, whereas the carbonate
dianion is a bridging ligand in the dinuclear [Ru2(µ-
O2CO)4]3– anion[21–23] and in polynuclear, heteroleptic
ruthenium complexes.[9,24,25]
The involvement of carbonatoruthenium complexes in
organometallic synthesis is still uncommon but, remarkably,
the carbonato complex [Ru(η2-O2CO)(bipy)2] has been
shown to react with terminal alkynes under aqueous acidic
conditions to conveniently produce [Ru(alkyl)(CO)(bipy)2]+
and [Ru(acyl)(CO)(bipy)2]+ derivatives.[26–28] We wish to re-
port here the direct synthesis of [Ru(η2-O2CO)(η6-ar-
ene)(PR3)] carbonatoruthenium() derivatives starting from
[RuCl2(η6-arene)(PR3)] precursors and K2CO3, and of re-
lated [Ru(η2-O2CO)(η6-arene)(IMes)] complexes, where
IMes is an imidazolylidene ligand, from [RuCl2(η6-arene)]2
precursors and an imidazolium salt in the presence of
K2CO3. The present account illustrates the usefulness of the
carbonato ligand as a protecting group for ruthenium
centres that favours the access to valuable ruthenium hy-
dride derivatives, such as the dihydride complex [RuH2-
Introduction
The formation of metal catalysts in situ from a metal
complex and an alkali metal carbonate salt, introduced as
a base, is receiving growing attention. This is the case with
a variety of cross-coupling and Heck reactions catalysed by
palladium complexes.[1,2] Recently, the generation of ruthe-
nium catalysts for ring-closing enyne metathesis[3,4] or se-
quential alkene isomerisation/Claisen reactions,[5] by treat-
ment of [RuCl2(η6-arene)]2 with an imidazolium salt and
Cs2CO3 in situ, has provided other useful examples. In this
case, Cs2CO3 was expected to generate an imidazolylidene
carbene by deprotonation of the imidazolium salt, as was
fully demonstrated by Arduengo[6] and Çetinkaya.[7] How-
ever, the question was raised whether the carbonate anion
acts solely as a proton acceptor or might additionally enter
into the coordination sphere of the ruthenium centre. In-
deed, there are already examples of carbonatoruthenium()
complexes, although such complexes were most often de-
picted as unexpected or undesired side-products. Their for-
mation has been observed during the course of various pro-
cesses, including metathetical exchange between an alkali
[a] Institut de Chimie de Rennes, UMR-CNRS 6509, Organomé-
talliques et Catalyse, Université de Rennes 1,
35042 Rennes Cedex, France
Fax: +33-22-323-6939
E-mail: bernard.demerseman@univ-rennes1.fr
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Direct Preparation of [Ru(η2-O2CO)(η6-arene)(L)] Carbonate Complexes
FULL PAPER
(p-cymene)(PCy3)], and to dicationic [Ru(η6-arene)(L)-
(MeCN)2][BF4]2 derivatives.
Results and Discussion
Synthesis of [Ru(η2-O2CO)(η6-arene)(L)] Complexes
Upon stirring at room temperature, a red slurry con-
sisting of [RuCl2(p-cymene)(PCy3)] (1a) and K2CO3 in ace-
tone as solvent gradually (2 d) turned yellow. Subsequent
workup afforded orange-yellow crystals of the new car-
bonato complex [Ru(η2-O2CO)(p-cymene)(PCy3)] (2a) in
78% yield (Scheme 1).
Scheme 2. Synthesis of the ruthenium hydride complexes 3a and
4a.
The formation of a metal alkoxide intermediate that
spontaneously undergoes a β-elimination process is among
the most usual routes allowing the transformation of metal–
halide into metal–hydride bonds. Evidence for such a
mechanism was first obtained from the study of the reac-
tion of [RuCl(Cp)(PPh3)2] with NaOMe,[29] and the synthe-
sis of [RuH(Cp)(PPh3)2] has since been more conveniently
achieved using K2CO3 in methanol.[30] The formation of
the hydride derivatives 3a and 4a that occurs in methanol
can be rationalised in the same way. The use of acetone as
solvent precludes the formation of any ruthenium methox-
ide intermediate and thus allows selective formation of 2a.
The conversion of 2a into the dihydride complex 3a that
occurs in methanol at reflux might result from the reaction
of the carbonato ligand with two molecules of methanol to
Scheme 1. Synthesis of the new carbonatoruthenium complexes
2a–d.
No reaction was detected under similar conditions start- generate methoxide groups along with carbon dioxide and
ing from [RuCl2(p-cymene)(PR3)] precursors 1b,c (b: R = water. Finally, the second minor compound, identified as
Ph; c: R = Me) without the addition of a small amount of the chloro hydride [RuCl(H)(p-cymene)(PCy3)] (4a), was al-
water to the reaction mixture (ca. 2 wt.-% relative to ace- ternatively synthesised by mixing equimolar amounts of 1a
tone) to promote the expected reaction and the formation and 3a in methanol as solvent (Scheme 2). The synthesis of
of complexes 2b,c (Scheme 1). Complexes 2b,c were isolated the parent complex [RuCl(H)(η6-benzene)(PCy3)] has re-
as orange solids in 97 and 95% yield, respectively. Since cently been achieved by treating [RuCl2(η6-benzene)(PCy3)]
very long reaction times (10 d starting from 1c) were re- with sodium formate.[31]
quired, the use of methanol (instead of acetone) as a polar
As with the reaction with 1c, the conversion of the more
solvent to facilitate the cleavage of ruthenium–chloride robust precursor [RuCl2(hexamethylbenzene)(PMe3)] (1d)
bonds was attempted. Starting from 1b,c, an obvious de- into the corresponding carbonato complex [Ru(η2-
composition was observed at room temperature, whereas 1a O2CO)(η6-C6Me6)(PMe3)] (2d) needed a reaction time
still led to 2a but also gave minor amounts of the dihydride longer than 10 d at room temperature. The synthesis of 2d
[RuH2(p-cymene)(PCy3)] (3a) and the chloro hydride was more rapidly (24 h) achieved by treating 1d with K2CO3
[RuCl(H)(p-cymene)(PCy3)] (4a), as determined by 31P{1H} in THF at reflux, although addition of a small amount of
NMR spectroscopy. When the yellow reaction mixture in water was also required to reach completion of the reaction
methanol was additionally heated at reflux for 1 h, the dihy- (Scheme 1).
dride 3a was obtained selectively (Scheme 2). The dihydride
The new complexes 2a–d, 3a and 4a were characterised
1
complex 3a was isolated as a colourless solid in yields of up by H, 13C, 13C{1H} and 31P{1H} NMR spectroscopy and
to 81%. As expected, 3a was also obtained when a solution elemental analysis. The H and 31P{1H} NMR spectra ac-
1
of pure 2a in methanol was heated at reflux (Scheme 2).
counted for the coordination of the phosphane besides the
Eur. J. Inorg. Chem. 2006, 1174–1181
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B. Demerseman, M. D. Mbaye, D. Sémeril, L. Toupet, C. Bruneau, P. H. Dixneuf
FULL PAPER
arene ligand. More specific and characteristic were the
1
high-field H NMR resonances corresponding to the RuH
protons in 3a and 4a. The presence of the carbonato ligand
in 2a–d was confirmed by 13C and 13C{1H} NMR spec-
troscopy as a resonance between δ = 165.6 and 166.8 ppm
with a small coupling constant (3JP,C Ͻ 2.9 Hz). The two
complexes 2a·1/2CH2Cl2 and 2d·H2O were further charac-
terised by an X-ray crystal structure analysis. Crystallo-
graphic data are summarised in the Exp. Sect., and ORTEP
drawings of 2a and 2d are shown in Figures 1 and 2, respec-
tively; selected bond lengths and angles are given in the cap-
tions.
Figure 2. ORTEP drawing of 2d·H2O showing 50% probability
thermal ellipsoids. The H2O molecule has been omitted for clarity.
Selected bond lengths [Å] and angles [°]: Ru1–O1 2.104(2), Ru1–
O2 2.091(2), O1–C13 1.325(4), O2–C13 1.315(4), O3–C13 1.239(4),
Ru1–P1 2.343(1); O1–Ru1–O2 62.81(8), C13–O1–Ru1 92.2(2),
C13–O2–Ru1 93.1(2), O1–C13–O2 111.8(2), O1–C13–O3 123.7(3),
O2–C13–O3 124.5(3), O1–Ru1–P1 88.61(7), O2–Ru1–P1 84.25(7).
to the Ru–P bond [2a: O1–Ru1–P1 = 86.92(5)°, O2–Ru1–
P1 = 88.09(5)°; 2d: O1–Ru1–P1 = 88.61(7)°, O2–Ru1–P1 =
84.25(7)°]. The Ru–P bond lengths in 2a and 2d are also
similar [2.3779(6) and 2.343(1) Å, respectively]. Finally,
these main structural features for the Ru(η2-O2CO) frag-
ment in 2a and 2d are in good agreement with those arising
from the study of the distinct complex [Ru(CO3)(PPh3)2-
(CO)2], obtained by hydrolysis of the carbamato ligands in
[Ru(O2CNiPr2)2(PPh3)2(CO)2].[12]
The observed need for water to generate the carbonato
2–
complexes 2 suggests a lack of reactivity of the CO3 di-
anion. Furthermore, attempts to synthesise 2d using
KHCO3 instead of K2CO3 also showed the same need for
addition of water to trigger the reaction. Note that the re-
lated complex [Ru(CO3)(η6-C6Me6)(iPr2PCH2CH2OMe)]
Figure 1. ORTEP drawing of 2a·1/2CH2Cl2 showing 50% prob-
ability thermal ellipsoids. The CH2Cl2 molecule has been omitted
for clarity. Selected bond lengths [Å] and angles [°]: Ru1–O1 has been fortuitously synthesised from [RuCl(η6-
C6Me6)(η2-P,O-iPr2PCH2CH2OMe)][PF6] upon treatment
2.079(2), Ru1–O2 2.087(2), O1–C11 1.323(3), O2–C11 1.315(3),
O3–C11 1.232(3), Ru1–P1 2.3779(6); O1–Ru1–O2 62.90(7), C11–
with aqueous Na2CO3.[10] The addition of water might be
O1–Ru1 93.02(1), C11–O2–Ru1 92.90(1), O1–C11–O2 111.0(2),
expected to result in the additional presence of the more
O1–C11–O3 124.5(2), O2–C11–O3 124.5(2), O1–Ru1–P1 86.92(5),
O2–Ru1–P1 88.09(5).
reactive hydroxide anion, and this suggested the formation
of a Ru–OH bond in a chloride ligand substitution reaction
Figures 1 and 2 show mononuclear species containing a as the first step in this reaction. As depicted in Scheme 3,
carbonate dianion η2-O,O-coordinated to the ruthenium subsequent reaction between the basic hydroxide intermedi-
centre. The two Ru–O bond lengths are almost identical, ate and the acidic HCO3– anion completes the formation of
although they are slightly longer in 2d [2.104(2) and the carbonato complexes.
2.091(2) Å in 2d vs. 2.087(2) and 2.079(2) Å in 2a]. The two
An insertion of carbon dioxide into the Ru–OH bond
Ru–O bonds form a small angle [62.90(7)° in 2a; 62.81(8)° might also be considered. Indeed, the stable bicarbonato
in 2d]. The exocyclic C=O bond in 2a or 2d [1.232(3) and derivative [Ru(η1-OCO2H)(Me)(η6-C6Me6)(PMe3)] has
1.239(4) Å, respectively] is significantly shorter than the two been previously been obtained by treating the hydroxide
endocyclic C–O bonds [1.323(3) and 1.315(3) Å in 2a; complex [Ru(OH)(Me)(η6-C6Me6)(PMe3)] with carbon di-
1.325(4) and 1.315(4) Å in 2d]. It is worth noting the planar oxide.[32]
arrangement of the Ru(η2-O2CO) fragment, as indicated by
The reaction between K2CO3 and an imidazolium salt
the sum of the angles of the four-membered ring, and such as 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride
around the carbon atom, both of which are very close to has been shown to generate reactive imidazol-2-ylidene spe-
360° (359.8° and 360.0° for 2a and 359.9° and 360.0° for cies that can be trapped with sulfur.[6] This process ap-
2d, respectively). This plane is approximately perpendicular peared attractive to synthesise organometallic (vs. sulfide)
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Direct Preparation of [Ru(η2-O2CO)(η6-arene)(L)] Carbonate Complexes
FULL PAPER
Synthesis of Dicationic [Ru(η6-arene)(L)(MeCN)2][BF4]2
Derivatives
As previously reported for the reactivity study of the car-
bonato complex [Ru(η2-O2CO)(bipy)2],[26] double proton-
ation of the carbonato ligand in complexes 2a–f easily oc-
curs under acidic conditions to generate carbon dioxide,
water, and to formally release a 14-electron [Ru(η6-ar-
ene)(L)]2+ fragment. The derivatives [Ru(η6-arene)(L)-
(MeCN)2][BF4]2 (5a–f) were isolated in high yield (84–99%)
after treating 2a–f with 2 equiv. of HBF4 (as its dimethyl
ether adduct) in acetonitrile as solvent (Scheme 5).
Scheme 3. Rationale accounting for the formation of complexes 2
catalysed by water.
derivatives under similar conditions. Thus, treatment of a
2:1 [H(IMes)]Cl/[RuCl2(η6-arene)]2 mixture with an excess
of K2CO3 in THF at reflux led to the new carbonato com-
plexes 2e and 2f, which were isolated as dark-orange solids
in 79 and 46% yield, respectively (Scheme 4).
Scheme 5. Synthesis of the dicationic derivatives [Ru(η6-arene)(L)-
(MeCN)2][BF4]2 (5a–f).
Complexes 5a–f are robust yellow compounds that are
highly soluble in acetonitrile. They were characterised by
1H, 13C, 13C{1H} and 31P{1H} NMR spectroscopy and ele-
mental analysis. Remarkably, the 13C NMR resonance cor-
responding to the carbene carbon nucleus in 5e and 5f (δ =
163.7 and 164.1 ppm, respectively) is shifted upfield relative
to 2e and 2f (δ = 180.5 and 183.6 ppm, respectively). This
observation likely indicates a reduced back-donation from
the metal atom in 5e and 5f as compared to 2e and 2f,
which results in an enhanced imidazolium (vs. imidazolylid-
ene) character.[33] A study of analogous [Ru(η6-ben-
zene)(L)(MeCN)2]2+ complexes obtained by treatment of
[Ru(η6-benzene)(MeCN)3][OTf]2 with a phosphane has re-
cently been reported and emphasises the potential of such
complexes.[34]
Scheme 4. Synthesis of the carbonatoruthenium complexes [Ru(η2-
O2CO)(η6-arene)(IMes)] (2e and 2f).
Complexes 2e and 2f, which only differ from the car-
bonato complexes 2a–d by the presence of the 1,3-bis(2,4,6-
trimethylphenyl)imidazol-2-ylidene ligand instead of
a
phosphane, were characterised by 1H, 13C and 13C{1H}
NMR spectroscopy and elemental analysis. The 13C NMR
resonance corresponding to the carbene carbon nucleus in
2e and 2f is located at δ = 180.5 and 183.6 ppm, respectively.
The assignment of the 13C NMR resonance corresponding
to the carbonato ligand in 2e and 2f (δ = 166.4 and
166.2 ppm, respectively) was inferred by comparison with
2a–d.
Conclusions
The formation of the carbonato complexes [Ru(η2-
O2CO)(η6-arene)(IMes)] sheds new light on the preparation
The easy formation of carbonatoruthenium complexes
of catalysts for enyne metathesis and O-allyl isomerisation on reaction of K2CO3 with LnRuCl2 precursors in the pres-
reactions, which were generated in situ by heating a mixture ence of water constitutes a convenient method to remove
of [RuCl2(p-cymene)]2, imidazolium salt and an excess of the chloride ligands and to use the carbonato ligand as a
Cs2CO3 in toluene.[3–5] The transient formation of [RuCl2(p- protecting group for transition metal centres. Under acidic
cymene)(IMes)], which releases a reactive [RuCl2(IMes)] conditions, a clean elimination of the carbonato ligand
moiety, was postulated. The fact that the catalytic species takes place to formally generate a coordinatively unsatu-
may arise from an [Ru(CO3)(p-cymene)(IMes)] species rated dicationic moiety. Thus, the transformation of
rather than the [RuCl2(p-cymene)(IMes)] intermediate must [RuCl2(η6-arene)(L)] precursors into dicationic [Ru(η6-ar-
now be considered.
ene)(L)(MeCN)2][BF4]2 derivatives is achieved without any
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1177

B. Demerseman, M. D. Mbaye, D. Sémeril, L. Toupet, C. Bruneau, P. H. Dixneuf
6.7 Hz, 6 H, CHMe2), 2.00 (s, 3 H, MeC6H4), 2.49 (m, 1 H,
FULL PAPER
involvement of strong chloride scavengers such as silver or
thallium salts. The carbonato ligand also allows a conve-
nient route to useful dihydride complexes upon reaction
with methanol. Finally, the formation of carbonatoruthen-
ium intermediates may interfere in processes where a ruthe-
nium catalyst is generated in situ from a ruthenium dichlo-
ride complex and an alkali metal carbonate as base.
3
3
CHMe2), 5.12 (d, JH,H = 6.1 Hz, 2 H, C6H4), 5.20 (d, JH,H
=
6.2 Hz, 2 H, C6H4), 7.37–7.54 (m, 15 H, Ph) ppm. 13C{1H} NMR
(75.47 MHz, CD2Cl2): δ = 18.6 (s, MeC6H4), 22.9 (s, CHMe2), 31.8
2
2
(s, CHMe2), 87.1 (d, JP,C = 5.4 Hz, C6H4, 2 CH), 87.8 (d, JP,C
=
4.4 Hz, C6H4, 2 CH), 96.3 (s, CMe, p-cymene), 106.8 (s, CiPr, p-
2
cymene), 128.8 (d, JP,C = 9.9 Hz, Ph, ortho), 131.1 (s, Ph, para),
1
3
131.5 (d, JP,C = 44.8 Hz, Ph, ipso), 134.5 (d, JP,C = 9.7 Hz, Ph,
meta), 165.1 (s, CO3) ppm. 31P{1H} NMR (121.50 MHz, CD2Cl2):
δ = 33.0 ppm (s). C29H29O3PRu (557.60): calcd. C 62.47, H 5.24,
P 5.55; found C 62.33, H 5.30, P 5.30.
Experimental Section
[Ru(η2-O2CO)(p-cymene)(PMe3)] (2c): A mixture consisting of a
sample of 1c (1.50 g, 3.92 mmol), K2CO3 (1.00 g, 7.24 mmol), ace-
tone (40 mL) and water (0.50 mL) was stirred for 10 d. The re-
sulting yellow slurry was concentrated to dryness and the remain-
ing solid was extracted with dichloromethane (40 mL). The solu-
tion was filtered and the orange filtrate was slowly concentrated to
leave an orange, crystalline solid, which was found to be pure by
1H and 31P{1H} NMR spectroscopy. Yield: 1.38 g (95%).
Recrystallisation from an acetone/acetonitrile mixture afforded
dark-orange crystals. 1H NMR (300.13 MHz, CD2Cl2): δ = 1.17
General: The reactions were performed according to Schlenk-type
techniques. Commercial solvents (99+% grade) were used without
further purification except diethyl ether and dichloromethane,
which were distilled under an inert gas after drying according to
conventional methods. NMR spectra were recorded at 297 K with
AC 200 FT and AC 300 Bruker instruments and referenced intern-
ally to the solvent peak. Elemental analyses were performed by the
“Service de Microanalyse du CNRS”, Vernaison, France. Com-
plexes 1a–d were obtained by treating the appropriate phosphane
with dimeric [RuCl2(η6-arene)]2 ruthenium complexes in dichloro-
methane as solvent, as described in the literature.[35] For the conve-
nience of this work, 1a was prepared as its acetone adduct. The
preparation of 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride
has been described elsewhere.[36]
3
2
(d, JH,H = 6.9 Hz, 6 H, CHMe2), 1.34 (d, JP,H = 10.3 Hz, 9 H,
PMe3), 2.05 (s, 3 H, MeC6H4), 2.51 (m, 1 H, CHMe2), 5.38 (d,
3
3JH,H = 5.9 Hz, 2 H, C6H4), 5.46 (d, JH,H = 5.9 Hz, 2 H, C6H4)
1
ppm. 13C{1H} NMR (75.47 MHz, CD2Cl2): δ = 14.9 (d, JP,C
=
28.4 Hz, PMe3), 18.9 (s, MeC6H4), 23.2 (s, CHMe2), 32.2 (s,
CHMe2), 86.1 (s, C6H4, 2 CH), 86.6 (s, C6H4, 2 CH), 94.9 (s, CMe,
p-cymene), 103.9 (s, CiPr, p-cymene), 166.7 (d, 3JP,C = 2.9 Hz, CO3)
ppm. 31P{1H} NMR (121.50 MHz, CD2Cl2): δ = 8.3 ppm (s).
C14H23O3PRu (371.38): calcd. C 45.28, H 6.24, P 8.34; found C
45.18, H 6.29, P 8.30.
[RuCl2(p-cymene)(PCy3)]·acetone (1a): Stoichiometric amounts of
[RuCl2(p-cymene)]2 (8.07 g, 13.2 mmol) and PCy3 (7.39 g,
26.4 mmol) were mixed in dichloromethane (60 mL) as reported
previously.[37] After stirring for 2 h, the mixture was concentrated
to dryness and acetone (60 mL) was added to the residue. The mix-
ture was stirred to obtain a red precipitate that was collected by
filtration. Yield: 16.1 g (95%). The product retains 1 equiv. of ace-
[Ru(η2-O2CO)(hexamethylbenzene)(PMe3)]·H2O (2d): A mixture
consisting of a sample of 1d (2.00 g, 4.87 mmol), K2CO3 (1.50 g,
10.9 mmol), acetone (40 mL) and water (0.60 mL) was stirred for
10 d. The resulting yellow slurry was concentrated to dryness and
the remaining solid was extracted with dichloromethane (40 mL).
Acetone (10 mL) was added to the orange filtrate and this mixture
was slowly concentrated to leave an orange, crystalline solid, which
was found to be pure by 1H and 31P{1H} NMR spectroscopy.
Yield: 1.87 g (92%). Alternatively, a mixture consisting of a sample
of 1d (1.00 g, 2.44 mmol), K2CO3 (1.00 g, 7.2 mmol), THF (40 mL)
and water (0.50 mL) was heated at reflux for 24 h, then treated as
above. Yield: 0.55 g (54%). Recrystallisation by diffusion of THF
into a concentrated solution of the compound in dichloromethane
afforded orange-red crystals. 1H NMR (300.13 MHz, CD2Cl2): δ =
1
tone per Ru, as indicated by H NMR spectroscopy.
[Ru(η2-O2CO)(p-cymene)(PCy3)]·1/2CH2Cl2 (2a): A mixture con-
sisting of a sample of 1a (6.00 g, 9.30 mmol), K2CO3 (2.00 g,
14.5 mmol) and acetone (50 mL) was stirred for 2 d. The volatiles
were then removed under vacuum to leave a yellow solid, whicht
was extracted with dichloromethane (50 mL). The solution was fil-
tered and the filtrate was covered with acetone (20 mL) and then
with diethyl ether (160 mL) to afford orange-yellow crystals. Yield:
1
3
4.51 g (78%). H NMR (300.13 MHz, CD2Cl2): δ = 1.25 (d, JH,H
= 6.9 Hz, 6 H, CHMe2), 1.16–1.89 (m, 33 H, Cy), 2.12 (s, 3 H,
3
Me), 2.52 (m, 1 H, CHMe2), 5.26 (d, JH,H = 6.2 Hz, 2 H, C6H4),
5.34 (d, JH,H = 6.2 Hz, 2 H, C6H4) ppm. 13C{1H} NMR
3
(75.47 MHz, CD2Cl2): δ = 18.7 (s, MeC6H4), 23.3 (s, CHMe2), 27.0
(s, Cy, 1 C), 28.3 (d, JP,C = 10.2 Hz, Cy, 2 C), 29.9 (s, Cy, 2 C),
2
1.22 (d, JP,H = 10.2 Hz, 9 H, PMe3), 2.04 (s, 18 H, C6Me6) ppm.
13C{1H} NMR (75.47 MHz, CD2Cl2): δ = 13.7 (d, 1JP,C = 28.0 Hz,
1
2
32.6 (s, CHMe2), 35.4 (d, JP,C = 18.9 Hz, Cy, 1 C), 85.4 (d, JP,C
2
2
PMe3), 16.2 (s, C6Me6), 95.1 (d, JP,C = 3.4 Hz, C6Me6), 166.8 (d,
= 3.8 Hz, C6H4, 2 CH), 86.6 (d, JP,C = 4.2 Hz, C6H4, 2 CH), 94.5
3JP,C = 2.6 Hz, CO3) ppm. 31P{1H} NMR (121.50 MHz, CD2Cl2):
δ = 4.7 ppm (s). C16H27O3PRu·H2O (417.45): calcd. C 46.04, H
7.00, P 7.42; found C 45.86, H 6.92, P 7.45.
3
(s, CMe, p-cymene), 103.7 (s, CiPr, p-cymene), 165.6 (d, JP,C
=
2.6 Hz, CO3) ppm. 31P{1H} NMR (121.50 MHz, CD2Cl2): δ =
37.8 ppm (s). C29H47O3PRu·1/2CH2Cl2 (618.21): calcd. C 57.32, H
7.66, Cl 5.73, P 5.01; found C 57.24, H 7.82, Cl 5.52, P 5.18.
[Ru(η2-O2CO)(p-cymene)(IMes)] (2e): A mixture consisting of a
[Ru(η2-O2CO)(p-cymene)(PPh3)] (2b): A mixture consisting of a sample of [RuCl2(p-cymene)]2 (2.00 g, 3.27 mmol), 1,3-bis(2,4,6-tri-
sample of 1b (2.71 g, 4.77 mmol), K2CO3 (1.50 g, 10.9 mmol), ace-
tone (40 mL) and water (0.50 mL) was stirred for 3 d. The resulting
yellow slurry was concentrated to dryness and the remaining solid
was extracted with dichloromethane (40 mL). Acetone (10 mL) was
added to the orange filtrate and this mixture was slowly concen-
trated to leave a crystalline orange-yellow solid, which was found
to be pure by 1H and 31P{1H} NMR spectroscopy. Yield: 2.57 g
methylphenyl)imidazolium chloride (2.27 g, 6.66 mmol), K2CO3
(3.00 g, 21.7 mmol), THF (40 mL) and dichloromethane (10 mL)
was stirred overnight then heated at reflux for 20 h. The resulting
slurry was concentrated to dryness and the remaining solid was
extracted with dichloromethane (30 mL). The solution was filtered
and the filtrate was concentrated under vacuum to leave a brown
solid, which was found to be pure by 1H NMR spectroscopy. Yield:
3.60 g (79%). Recrystallisation from hot toluene afforded dark-
orange crystals of 2e·1/4C7H8 in 77% yield relative to crude 2e. 1H
(97%). Orange crystals were obtained by recrystallisation from hot
3
acetonitrile. 1H NMR (300.13 MHz, CD2Cl2): δ = 1.18 (d, JH,H
=
1178
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 1174–1181

Direct Preparation of [Ru(η2-O2CO)(η6-arene)(L)] Carbonate Complexes
FULL PAPER
3
NMR (300.13 MHz, CD2Cl2): δ = 0.76 (d, JH,H = 6.9 Hz, 6 H,
tion of 4a. Recrystallisation by dissolution in dichloromethane
CHMe2), 1.28 (s, 3 H, MeC6H4), 1.56 (m, 1 H, CHMe2), 2.08 (s, (25 mL) and then diffusion of methanol (100 mL) afforded dark-
12 H, Mes, 4 Me), 2.25 (s, toluene), 2.27 (s, 6 H, Mes, 2 Me), 4.74 orange crystals but in a moderate yield (0.94 g, 39%) owing to re-
(d, 3JH,H = 6.1 Hz, 2 H, C6H4), 5.04 (d, 3JH,H = 6.2 Hz, 2 H, C6H4), sidual solubility. 1H NMR (300.13 MHz, CD2Cl2): δ = –8.0 (d,
6.93 (s, 2 H, CH=), 6.93 (s, 2 H, Mes, 2 CH), 6.94 (s, 2 H, Mes,
2 CH), 7.04–7.15 (m, toluene) ppm. 13C{1H} NMR (75.47 MHz,
CD2Cl2): δ = 17.1 (s, MeC6H4), 18.7 (s, Mes, 4 Me), 21.2 (s,
CHMe2), 23.4 (s, Mes, 2 Me), 32.2 (s, CHMe2), 84.5 (s, C6H4, 2 1 H, C6H4), 4.48 (d, JH,H = 6.1 Hz, 1 H, C6H4), 6.05 (m, 2 H,
CH), 85.2 (s, C6H4, 2 CH), 94.7 (s, CMe, p-cymene), 100.3 (s, CiPr, C6H4) ppm. 13C{1H} NMR (75.47 MHz, CD2Cl2): δ = 19.5 (s,
p-cymene), 125.2 (s, NCH=), 129.2 (s, Mes, 4 CH), 136.9 (s, Mes, MeC6H4), 21.2 (s, CHMe2), 25.4 (s, CHMe2), 27.3 (s, Cy, 1 C), 28.3
2JP,H = 49.5 Hz, 1 H, RuH), 1.12 (d, 3JH,H = 7.0 Hz, 3 H, CHMe2),
3
1.26 (d, JH,H = 6.8 Hz, 3 H, CHMe2), 1.06–1.90 (m, 33 H, Cy),
3
1.95 (s, 3 H, Me), 2.14 (m, 1 H, CHMe2), 4.28 (d, JH,H = 5.4 Hz,
3
4 CMe), 137.1 (s, Mes, 2 CN), 139.3 (s, Mes, 2 CMe), 166.4 (s,
(d, JP,C = 9.9 Hz, Cy, 1 C), 28.4 (d, JP,C = 10.9 Hz, Cy, 1 C), 30.0
(s, Cy, 1 C), 30.1 (d, JP,C = 1.8 Hz, Cy, 1 C), 31.7 (s, CHMe2), 36.8
CO3), 180.5 (s, Ru=C) ppm; the resonances of toluene have been
omitted. C32H41N2O3Ru·1/4C7H8 (625.80): calcd. C 64.78, H 6.60, (d, 1JP,C = 21.8 Hz, Cy, 1 C), 79.6 (d, 2JP,C = 2.7 Hz, C6H4, 1 CH),
N 4.48; found C 64.73, H 6.54, N 4.16.
86.7 (d, 2JP,C = 4.5 Hz, C6H4, 1 CH), 86.9 (d, 2JP,C = 5.4 Hz, C6H4,
2
1 CH), 91.2 (d, JP,C = 3.6 Hz, C6H4, 1 CH), 97.8 (s, CMe, p-
[Ru(η2-O2CO)(hexamethylbenzene)(IMes)] (2f): A mixture con-
cymene), 106.5 (s, CiPr, p-cymene) ppm. 31P{1H} NMR (CD2Cl2):
δ = 59.7 ppm (s). C28H48ClPRu (552.19): calcd. C 60.90, H 8.76,
Cl 6.42, P 5.61; found C 60.89, H 9.06, Cl 6.68, P 5.74.
sisting of
a sample of [RuCl2(hexamethylbenzene)]2 (1.50 g,
2.24 mmol), 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride
(1.52 g, 4.46 mmol), K2CO3 (1.00 g, 7.24 mmol) and THF (40 mL)
was stirred overnight, then heated at reflux for 24 h. The resulting
slurry was concentrated to dryness and the remaining solid was
extracted with dichloromethane (30 mL). The solution was filtered
and the filtrate was concentrated under vacuum to leave a brown
solid. Yield: 1.30 g (46%). Dark-orange crystals were obtained
[Ru(p-cymene)(PCy3)(MeCN)2][BF4]2 (5a): Complexes 5a–f were
quantitatively formed by treating the corresponding carbonato
complex in solution in cold acetonitrile with a stoichiometric
amount of HBF4·OMe2. In a typical procedure, a 1.2  solution of
HBF4·OMe2 in methanol (7.5 mL, 9.0 mmol) was added to a
stirred solution of 2a (2.75 g, 4.45 mmol) in cold acetonitrile
1
from hot toluene. H NMR (300.13 MHz, CD2Cl2): δ = 1.55 (s, 18
H, C6Me6), 2.09 (s, 6 H, Mes, 2 Me), 2.10 (s, 6 H, Mes, 2 Me), 2.27 (30 mL, –40 °C). The mixture was allowed to reach room tempera-
(s, 6 H, Mes, 2 Me), 6.83 (s, 2 H, CH=), 6.90 (s, 2 H, Mes, 2
ture (1 h) and then concentrated under vacuum. The resulting solu-
tion was covered with dichloromethane (20 mL) and then diethyl
CH), 6.92 (s, 2 H, Mes, 2 CH) ppm. 13C{1H} NMR (75.47 MHz,
CD2Cl2): δ = 15.6 (s, C6Me6), 19.1 (s, Mes, 2 Me ortho), 19.5 (s, ether (120 mL) to afford yellow crystals. Yield: 3.26 g (95%). 1H
Mes, 2 Me ortho), 21.2 (s, Mes, 2 Me para), 92.9 (s, C6Me6), 125.1
3
NMR (300.13 MHz, CD3CN): δ = 1.41 (d, JH,H = 6.9 Hz, 6 H,
(s, NCH=), 128.2 (s, Mes, 2 CH), 129.5 (s, Mes, 2 CH), 135.0 (s, CHMe2), 1.48–1.94 (m, broad, 33 H, Cy), 2.10 (s, 6 H, MeCN),
3
Mes, 2 CMe ortho), 137.6 (s, Mes, 2 CN), 138.7 (s, Mes, 2 CMe
para), 139.0 (s, Mes, 2 CMe ortho), 166.2 (s, CO3), 183.6 (s, Ru=C)
2.27 (s, 3 H, MeC6H4), 2.80 (m, 1 H, CHMe2), 6.34 (d, JH,H =
3
6.6 Hz, 2 H, C6H4), 6.42 (d, JH,H = 6.6 Hz, 2 H, C6H4) ppm.
ppm. 13C NMR (75.47 MHz, CD2Cl2, selected values): δ = 13C{1H} NMR (75.47 MHz, CD2Cl2): δ = 4.76 (s, MeCN), 18.9 (s,
1
3
125.1 ppm (dd, JH,C
=
196, JH,C
=
11.9 Hz, NCH=).
MeC6H4), 22.6 (s, CHMe2), 26.5 (s, Cy, 1C), 27.7 (d, JP,C = 10.3 Hz,
Cy, 2 C), 30.4 (d, JP,C = 1.7 Hz, Cy, 2 C), 32.2 (s, CHMe2), 37.9
(d, JP,C = 19.8 Hz, Cy, 1 C), 90.8 (d, JP,C = 2.9 Hz, C6H4, 2 CH),
C34H42N2O3Ru (627.79): calcd. C 65.05, H 6.74, N 4.46; found C
64.72, H 6.57, N 4.56.
2
2
93.0 (d, JP,C = 1.7 Hz, C6H4, 2 CH), 103.9 (s, CMe, p-cymene),
[RuH2(p-cymene)(PCy3)] (3a): A mixture consisting of a sample of
1a (3.29 g, 5.11 mmol), K2CO3 (1.50 g, 10.9 mmol) and methanol
(40 mL) was stirred at room temperature for 0.5 h and the resulting
yellow slurry was heated at reflux for 1 h. The hot solution was
immediately filtered and the brown filtrate was concentrated under
vacuum to leave a solid, which was washed twice with cold meth-
anol to give a colourless, crystalline powder. Yield: 2.13 g (81%).
Similarly, a solution of 2a in methanol was heated at reflux for
1 h and then treated as above to give 3a in 70% yield. 1H NMR
114.3 (s, CiPr, p-cymene), 132.2 (s, MeCN) ppm. 31P{1H} NMR
(121.50 MHz, CD2Cl2): δ = 44.7 ppm (s). C32H53B2F8N2PRu
(771.44): calcd. C 49.82, H 6.93, N 3.63, P 4.02; found C 49.59, H
7.03, N 3.64, P 4.38.
[Ru(p-cymene)(PPh3)(MeCN)2][BF4]2 (5b): Yield: 96%, yellow crys-
tals. 1H NMR (300.13 MHz, CD3CN): δ = 1.36 (d, 3JH,H = 6.3 Hz,
6 H, CHMe2), 1.94 (s, 3 H, MeC6H4), 2.33 (s, 6 H, MeCN), 2.94
(m, 1 H, CHMe2), 5.63 (dd, 3JH,H = 6.7, 3JP,H = 1.3 Hz, 2 H, C6H4),
6.27 (d, 3JH,H = 6.6 Hz, 2 H, C6H4), 7.66–7.77 (m, 15 H, Ph) ppm.
13C{1H} NMR (75.47 MHz, CD3CN): δ = 4.66 (s, MeCN), 18.7 (s,
2
(300.13 MHz, C6D6): δ = –11.0 (d, JP,H = 43.3 Hz, 2 H, RuH),
3
1.29 (d, JH,H = 6.7 Hz, 6 H, CHMe2), 1.17–2.06 (m, 33 H, Cy),
3
2.08 (s, 3 H, Me), 2.46 (m, 1 H, CHMe2), 5.07 (d, JH,H = 5.6 Hz,
MeC6H4), 22.3 (s, CHMe2), 32.3 (s, CHMe2), 92.5 (s, C6H4, 2 CH),
3
2
2 H, C6H4), 5.16 (d, JH,H = 5.6 Hz, 2 H, C6H4) ppm. 13C{1H} 93.9 (d, JP,C = 2.9 Hz, C6H4, 2 CH), 107.6 (s, CMe, p-cymene),
NMR (75.47 MHz, C6D6): δ = 21.7 (s, MeC6H4), 25.3 (s, CHMe2),
27.7 (s, Cy, 1 C), 28.7 (d, JP,C = 9.8 Hz, Cy, 2 C), 31.2 (s, Cy, 2 C), (d, JP,C = 10.2 Hz, Ph, ortho), 132.2 (s, MeCN), 133.3 (d, JP,C
119.3 (s, CiPr, p-cymene), 129.6 (d, 1JP,C = 51.9 Hz, Ph, ipso), 130.5
2
4
=
1
2
3
33.5 (s, CHMe2), 40.0 (d, JP,C = 21.8 Hz, Cy, 1 C), 80.0 (d, JP,C 2.9 Hz, Ph, para), 134.9 (d, JP,C = 10.2 Hz, Ph, meta) ppm.
2
= 3.8 Hz, C6H4, 2 CH), 85.7 (d, JP,C = 1.7 Hz, C6H4, 2 CH), 96.9
(s, CMe, p-cymene), 110.4 (s, CiPr, p-cymene) ppm. 31P{1H} NMR
(121.50 MHz, C6D6) δ = 78.1 ppm (s). C28H49PRu (517.74): calcd.
C 64.96, H 9.54, P 5.98; found C 64.79, H 9.50, P 5.87.
31P{1H} NMR (121.50 MHz, CD3CN):
δ = 39.4 ppm (s).
C32H35B2F8N2PRu (753.30): calcd. C 51.02, H 4.68, N 3.72, P 4.11;
found C 50.78, H 4.68, N 3.72, P 4.10.
[Ru(p-cymene)(PMe3)(MeCN)2][BF4]2 (5c): Yield: 88%, lemon-yel-
1
3
[RuCl(H)(p-cymene)(PCy3)] (4a): Equimolar amounts of 3a (1.14 g,
2.20 mmol) and 1a (1.42 g, 2.20 mmol) were added to methanol
(30 mL) and this mixture was stirred at room temperature over-
night (or heated at reflux for 1 h) to afford a yellow slurry. Concen-
tration of the mixture and subsequent analysis of the residue by 1H
and 31P{1H} NMR spectroscopy indicated a quantitative forma-
low crystals. H NMR (300.13 MHz, CD3CN): δ = 1.32 (d, JH,H
= 6.9 Hz, 6 H, CHMe2), 1.84 (d, 2JP,H = 12.0 Hz, 9 H, PMe3), 2.20
5
(s, 3 H, MeC6H4), 2.63 (d, JP,H = 1.3 Hz, 6 H, MeCN), 2.80 (m,
1 H, CHMe2), 6.27 (m, 4 H, C6H4) ppm. 13C{1H} NMR
1
(75.47 MHz, CD3CN): δ = 4.82 (s, MeCN), 16.7 (d, JP,C
=
34.7 Hz, PMe3), 18.6 (s, MeC6H4), 22.2 (s, CHMe2), 32.0 (s,
Eur. J. Inorg. Chem. 2006, 1174–1181
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1179

B. Demerseman, M. D. Mbaye, D. Sémeril, L. Toupet, C. Bruneau, P. H. Dixneuf
FULL PAPER
2
2
1
3
CHMe2), 91.7 (d, JP,C = 4.0 Hz, C6H4, 2 CH), 94.5 (d, JP,C
=
(dd, JH,C = 201, JH,C = 12 Hz, NCH=). C35H44B2F8N4Ru
3.3 Hz, C6H4, 2 CH), 102.9 (s, CMe, p-cymene), 113.0 (s, CiPr, p-
(795.44): calcd. C 52.85, H 5.58, N 7.04; found C 52.68, H 5.62, N
cymene), 130.5 (s, MeCN) ppm. 31P{1H} NMR (121.50 MHz, 6.99.
CD3CN): δ = 12.5 ppm (s). C17H29B2F8N2PRu (567.08): calcd. C
[Ru(hexamethylbenzene)(IMes)(MeCN)2][BF4]2 (5f): Yield: 84%,
36.01, H 5.15, N 4.94, P 5.46; found C 35.74, H 5.19, N 4.95, P
5.83.
1
orange crystals. H NMR (200.13 MHz, CD3CN): δ = 1.78 (s, 18
H, C6Me6), 1.95 (s, 6 H, MeCN), 2.06 (s, 12 H, Mes, 4 Me), 2.35
(s, 6 H, Mes, 2 Me), 7.11 (s, Mes, 4 H), 7.25 (s, 2 H, CH=) ppm.
13C{1H} NMR (75.47 MHz, CD2Cl2): δ = 5.30 (s, MeCN), 16.5 (s,
[Ru(hexamethylbenzene)(PMe3)(MeCN)2][BF4]2 (5d): Yield: 92%,
1
lemon-yellow crystals. H NMR (300.13 MHz, CD3CN): δ = 1.55
2
(d, JP,H = 11.5 Hz, 9 H, PMe3), 2.17 (s, 18 H, C6Me6), 2.52 (d, C6Me6), 18.7 (s, Mes, 4 Me), 21.2 (s, Mes, 2 Me), 101.7 (s, C6Me6),
5JP,H = 1.3 Hz, 6 H, MeCN) ppm. 13C{1H} NMR (75.47 MHz,
CD3CN): δ = 4.79 (s, MeCN), 14.8 (d, 1JP,C = 33.5 Hz, PMe3), 16.6
128.5 (s, NCH=), 129.3 (s, MeCN), 130.3 (s, Mes, 4 CH), 136.1 (s,
Mes, 4 CMe), 137.1 (s, Mes, 2 CN), 141.1 (s, Mes, 2 CMe), 164.1
(s, C6Me6), 103.6 (d, 2JP,C = 1.9 Hz, C6Me6), 129.8 (s, MeCN) ppm. (s, Ru=C) ppm. 13C NMR (75.47 MHz, CD2Cl2, selected values):
31P{1H} NMR (121.50 MHz, CD3CN):
δ = 8.9 ppm (s). δ = 128.5 ppm (dd, JH,C = 201, JH,C = 11 Hz, NCH=).
1
3
C19H33B2F8N2PRu (595.14): calcd. C 38.35, H 5.59, N 4.71, P 5.20;
found C 38.32, H 5.66, N 4.69, P 5.40.
C37H48B2F8N4Ru (823.49): calcd. C 53.97, H 5.88, N 6.80; found
C 53.95, H 6.09, N 6.90.
[Ru(p-cymene)(IMes)(MeCN)2][BF4]2 (5e): Yield: 99%, orange crys-
X-ray Crystallography: A selected crystal of 2a·1/2CH2Cl2 was
studied with a NONIUS Kappa CCD diffractometer equipped
3
tals. 1H NMR (300.13 MHz, CD2Cl2): δ = 1.03 (d, JH,H = 6.9 Hz,
6 H, CHMe2), 1.73 (s, 3 H, MeC6H4), 1.97 (m, 1 H, CHMe2), 2.07 with a graphite monochromator. The cell parameters were obtained
(s, 12 H, Mes, 4 Me), 2.34 (s, 6 H, Mes, 2 Me), 2.36 (s, 6 H, MeCN),
with Denzo and Scalepack,[38] and data collection with NONIUS
5.41 (d, JH,H = 6.3 Hz, 2 H, C6H4), 5.71 (d, JH,H = 6.5 Hz, 2 H, KappaCCD software.[39] Data reduction was carried out with
C6H4), 7.10 (s, 4 H, Mes, CH), 7.27 (s, 2 H, CH=) ppm. 13C{1H} Denzo and Scalepack.[38] A selected crystal of 2d·H2O was studied
NMR (75.47 MHz, CD2Cl2): δ = 4.74 (s, MeCN), 18.3 (s, Mes, 4 with a NONIUS CAD 4 automatic diffractometer equipped with
Me), 18.6 (s, MeC6H4), 21.2 (s, Mes, 2 Me), 22.7 (s, CHMe2), 32.1 a graphite monochromator.[40] After Lorenz and polarisation cor-
(s, CHMe2), 90.6 (s, C6H4, 2 CH), 91.3 (s, C6H4, 2 CH), 104.5 (s, rections (2d),[41] the structures were solved with SIR-97, which re-
3
3
CMe, p-cymene), 109.0 (s, CiPr, p-cymene), 127.8 (s, NCH=), 129.5
(s, MeCN), 130.1 (s, Mes, 4 CH), 136.1 (s, Mes, 4 CMe), 136.4 (s,
Mes, 2 CN), 141.6 (s, Mes, 2 CMe, Mes), 163.7 (s, Ru=C) ppm.
vealed the non-hydrogen atoms.[42,43] After anisotropic refinement,
many hydrogen atoms might be found with Fourier difference cal-
culations. The whole structures were refined with SHELXL-97 by
13C NMR (75.47 MHz, CD2Cl2, selected values): δ = 127.8 ppm full-matrix least-squares methods on F2 (x, y, z, βij for Ru, P, Cl,
Table 1. Crystallographic data for complexes 2a·1/2CH2Cl2 and 2d·H2O.[a]
Complex
2a·1/2CH2Cl2
2d·H2O
Empirical formula
Molecular mass [gmol–1]
Crystal size [mm]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C59H96Cl2O6P2Ru2
1236.34
C16H29O4PRu
417.43
0.32×0.26×0.22
monoclinic
P21/n
12.900(4)
14.846(7)
9.764(3)
90
103.32(3)
90
1819.6(12)
4
1.524
0.32×0.22×0.20
triclinic
¯
P1
14.6292(3)
15.8474(3)
16.0019(3)
115.050(1)
114.131(1)
94.460(1)
2922.55(10)
2
γ [°]
Volume [Å3]
Z
Density [gcm–3]
Temperature [K]
F(000)
1.405
150(2)
1300
293(2)
864
Mo-Kα radiation, λ [Å]
Absorption coefficient [mm–1]
θ range [°]
0.71073
0.711
1.49 to 27.51
0 Ͻ h Ͻ 19
–20 Ͻ k Ͻ 20
–20 Ͻ l Ͻ 18
32238
0.71073
0.963
2.12 to 27.02
–16 Ͻ h Ͻ 16
0 Ͻ k Ͻ 18
0 Ͻ l Ͻ 12
4176
Index ranges
Reflections collected
Independent reflections
Reflections [I Ͼ 2σ(I)]
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)]
12228 (Rint = 0.0000)
10808
12923/0/641
1.088
R1 = 0.0328
wR2 = 0.0759
R1 = 0.0440
wR2 = 0.0832
0.837/–0.929
3951 (Rint = 0.0253)
3474
3951/0/200
1.018
R1 = 0.0320
wR2 = 0.0858
R1 = 0.0397
wR2 = 0.0895
0.869/–0.840
R indices (all data)
Largest diff. peak/hole [e·Å–3]
[a] w = 1/[σ2(Fo2) + (0.0252P)2 + 3.4483P] (2a), 1/[σ2(Fo2) + (0.0532P)2 + 2.1077P] (2d), where P = (Fo + 2Fc )/3.
2
2
1180 Eur. J. Inorg. Chem. 2006, 1174–1181
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Direct Preparation of [Ru(η2-O2CO)(η6-arene)(L)] Carbonate Complexes
FULL PAPER
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were detected. Further crystallographic data are given in Table 1.
CCDC-287581 (2a), and -287580 (2d) contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
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Received: November 2, 2005
Published Online: January 31, 2006
Eur. J. Inorg. Chem. 2006, 1174–1181
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1181