New octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] complexes containing one hemilabile ketophosphane ligand

Article abstract of DOI:10.1002/1099-0682(200109)2001:9<2347::AID-EJIC2347>3.0.CO;2-9

The reaction of the ketophosphanes Ph₂PCH₂C(=O)tBu (1), Ph₂PCMe₂C(=O)iPr (1′), or Ph₂PCMe₂CH₂C(=O)Me (1″) with a precursor complex RuCl₂(L)(η⁶-p-cymene) [L = PMe₃ (a), PMePh₂ (b), PiPrPh₂ (c), PPh₃ (d), P(OMe)Ph₂ (e), P(OMe)₃ (f)] in methanol and under carbon monoxide, provides an access to a novel family of complexes (ttt)-RuCl₂(CO)(L)[η²-(P,O)-ketophosphane] (2a-e, 2′a,e,f, and 2″a) with trans-chlorine and trans-phosphorus atoms. Further reaction with carbon monoxide or acetonitrile under thermal activation yields the cis,cis,trans derivatives (cct)-RuCl₂(CO)₂(L)[η¹-(P)- ketophosphane] 4a,b and 4′a, and (cct)-RuCl₂(CO)(MeCN)(L)[η¹-(P)-ketophosphane] 5a,b,d. Complexes 2a,b and 2′a rearrange under thermal activation, or after exposure to sunlight, into the (ctc and ccc)-RuCl₂(CO)(L)[η²-(P,O)-ketophosphane] isomers, with cis-chlorine and cis-phosphorus atoms, 6a,b and 6′a, respectively. Complexes 6a,b reversibly add one molecule of carbon monoxide when forming the all-cis derivatives (ccc)-RuCl₂(CO)₂(L)[η¹-(P)- ketophosphane] 7a,b, respectively. The removal of one chloride ligand in complexes 4a, 4′a, or 5a with silver tetrafluoroborate affords the stable cationic derivatives {RuCl(CO)(L′)(PMe₃)[η²-(P,O)- ketophosphane]}[BF₄], 8a and 8′a (L′ = CO) and 9a (L′ = MeCN), respectively. Mild basic conditions are sufficient to allow the synthesis of the enolatophosphane derivatives (ttt)-RuCl(CO)₂(L)[η²-(P,O)-Ph₂ PCH=C(tBu)O], 10a,c,e, and of the analogous (ccc) and (cct) isomers, 11a,b and 12a, respectively.

Full text of DOI:10.1002/1099-0682(200109)2001:9<2347::AID-EJIC2347>3.0.CO;2-9

FULL PAPER
New Octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] Complexes
Containing One Hemilabile Ketophosphane Ligand
Bernard Demerseman[a]
Keywords: Ruthenium / Phosphanes / O ligands / Carbonyl ligands / Isomerizations
The reaction of the ketophosphanes Ph2PCH2C(=O)tBu (1),
Ph2PCMe2C(=O)iPr (1Ј), or Ph2PCMe2CH2C(=O)Me (1ЈЈ)
RuCl2(CO)(L)[η2-(P,O)-ketophosphane] isomers, with cis-
chlorine and cis-phosphorus atoms, 6a,b and 6Јa, respect-
with a precursor complex RuCl2(L)(η6-p-cymene) [L = PMe3 ively. Complexes 6a,b reversibly add one molecule of carbon
(a), PMePh2 (b), PiPrPh2 (c), PPh3 (d), P(OMe)Ph2 (e),
monoxide when forming the all-cis derivatives (ccc)-
P(OMe)3 (f)] in methanol and under carbon monoxide, pro- RuCl2(CO)2(L)[η1-(P)-ketophosphane] 7a,b, respectively. The
vides an access to
a
novel family of complexes (ttt)-
removal of one chloride ligand in complexes 4a, 4Јa, or 5a
with silver tetrafluoroborate affords the stable cationic deriv-
atives {RuCl(CO)(LЈ)(PMe3)[η2-(P,O)-ketophosphane]}[BF4],
8a and 8Јa (LЈ = CO) and 9a (LЈ = MeCN), respectively. Mild
basic conditions are sufficient to allow the synthesis of the
enolatophosphane derivatives (ttt)-RuCl(CO)2(L)[η2-(P,O)-
Ph2PCH=C(tBu)O], 10a,c,e, and of the analogous (ccc) and
(cct) isomers, 11a,b and 12a, respectively.
RuCl2(CO)(L)[η2-(P,O)-ketophosphane] (2a−e, 2Јa,e,f, and
2ЈЈa) with trans-chlorine and trans-phosphorus atoms. Fur-
ther reaction with carbon monoxide or acetonitrile under
thermal activation yields the cis,cis,trans derivatives (cct)-
RuCl2(CO)2(L)[η1-(P)-ketophosphane] 4a,b and 4Јa, and
(cct)-RuCl2(CO)(MeCN)(L)[η1-(P)-ketophosphane]
Complexes 2a,b and 2Јa rearrange under thermal activation,
or after exposure to sunlight, into the (ctc and ccc)-
5a,b,d.
Introduction
comparison. Furthermore, under basic conditions they are
suspected of generating coordinatively unsaturated η2-
(P,O)-enolatophosphane derivatives by a formal HCl ab-
straction.
The discovery of the hemilabile behaviour of an
etherϪphosphane ligand,[1] in which the ether functionality
coordinates at a ruthenium centre, has undoubtedly stimu-
lated the interest of organometallic chemists with regard to
functional phosphanes. The complexation of such ligands
is of interest since the oxygenϪmetal bond is weak, thus
providing facile access to coordinative unsaturation.[2,3] The
series of RuCl2[η2-(P,O)-functional phosphane]2 complexes,
in which the organic function consists of an ether,[1,4Ϫ8] an
ester,[9Ϫ11] or a keto group, have been largely studied.[12,13]
Interestingly, their geometry is of type I (see Scheme 1),
consisting of trans-chlorine, cis phosphorus, and cis-oxygen
atoms, respectively. The preferred cis arrangement of the
phosphorus atoms is unusual, as emphasised by the ability
of complexes I to trap carbon monoxide through an irre-
versible process involving a cis-to-trans rearrangement of
the phosphorus atoms (Scheme 1). The resulting complexes
II exhibit a noteworthy fluxional behaviour through easy
exchange between the coordinating modes of the oxygen
Scheme 1
atoms (not depicted in Scheme 1) and are able to intercon- Results
vert with type-III complexes by reversible addition of car-
Synthesis of (ttt)-RuCl2(CO)(L)[η2-(P,O)-ketophosphane]
Complexes 2؊2ЈЈ
bon monoxide. We report herein a convenient route to new
hybrid (ttt)-RuCl2(CO)(L)[η2-(P,O)-ketophosphane] com-
plexes with trans-chlorine and trans-phosphorus atoms.
They are analogous of both type-II and all-trans
RuCl2(CO)2L2 complexes, and their study will allow further
An equimolar mixture consisting of a precursor complex
RuCl2(L)(η6-p-cymene) [L ϭ PMe3 (a), PMePh2 (b),
PiPrPh2 (c), PPh3 (d), P(OMe)Ph2 (e), P(OMe)3 (f)] and a
ketophosphane [Ph2PCH2C(ϭO)tBu (1), Ph2PCMe2C(ϭ
O)iPr (1Ј), Ph2PCMe2CH2C(ϭO)Me (1ЈЈ)] in methanol was
stirred at ambient temperature under carbon monoxide.
Subsequent workup allowed all-trans (based on two trans-
[a]
Laboratoire de Chimie de Coordination et Catalyse, UMR-
´
CNRS 6509, Campus de Beaulieu, Universite de Rennes I,
´
35042 Rennes Cedex, France
E-mail: Bernard.Demerseman@univ-rennes1.fr
Eur. J. Inorg. Chem. 2001, 2347Ϫ2359
WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001
1434Ϫ1948/01/0909Ϫ2347 $ 17.50ϩ.50/0
2347

B. Demerseman
FULL PAPER
chlorine and two trans-phosphorus atoms, respectively)
complexes
(ttt)-RuCl2(CO)(L)[η2-(P,O)-ketophosphane]
2aϪe, 2Јa,e,f, and 2ЈЈa, to be isolated in moderate to high
yields (49Ϫ84%) as orange air-stable crystals (except for 2d)
(Scheme 2). The reaction formally consists of the substitu-
tion of a 6e-donor ligand (p-cymene) by one molecule of
carbon monoxide and one molecule of ketophosphane act-
ing as a 4e-donor. The generality of the reaction is not only
shown by the involvement of a β- (1, 1Ј) or a γ-ketophos-
phane (1ЈЈ), but also by the ability of the precursor complex
RuCl2(η6-p-cymene)[η1-(P)-Ph2PCH2C(ϭO)tBu][14] in pro-
viding an alternative route to complexes of type 2, when
reacting with a ligand L such as P(OMe)Ph2 and with car-
bon monoxide, to afford the expected derivative 2e (see
Scheme 2). The permethylated β-ketophosphane 1Ј is un-
able to form
a
similar RuCl2(η6-p-cymene)[η1-(P)-
Ph2PCMe2C(ϭO)iPr] derivative, but reacts with dimeric
[RuCl2(η6-p-cymene)]2 in methanol to generate a cationic
species {RuCl(η6-p-cymene)[η2-(P,O)-Ph2PCMe2C(iPr)ϭ
O]}ϩ, which has previously been characterised as its PF6
salt.[14] Such solutions of {RuCl(η6-p-cymene)[η2-(P,O)-
Ph2PCMe2C(iPr)ϭO]}Cl in methanol may also be used to
synthesise complexes 2Ј. As summarised in Scheme 2, these
distinct pathways leading to complexes 2؊2ЈЈ may be ra-
tionalised in terms of the formation of a transient cationic
species {RuCl(η6-p-cymene)(L)[η1-(P)-ketophosphane]}ϩ
that will further react with carbon monoxide. Such a mech-
anism accounts for the requirement of methanol as the solv-
ent, which allows a transient cleavage of one RuϪCl bond.
The reaction does not work in a solvent such as CH2Cl2.
This strongly suggests the key role of methanol in the la-
bilisation of the RuϪCl bond.
The structures of complexes 2؊2ЈЈ were determined from
a combination of elemental analysis, IR spectroscopy and
1H, 31P{1H}, 13C{1H}, and 13C NMR spectroscopy. Ele-
mental analysis indicates the retention of two chlorine
atoms per Ru atom. The IR spectra (Table 1) exhibit a very
strong absorption close to 1940 cmϪ1 assigned to the car-
bon monoxide ligand, as well as a strong absorption close
to 1640 cmϪ1 (1673 cmϪ1 for 2ЈЈa) indicating the coordina-
Scheme 2
are 2a, 2Јa, and 2ЈЈa (in which L ϭ PMe3). They were unaf-
fected when thermally treated under reflux in methanol for
several hours. In contrast, 2e [in which L ϭ P(OMe)Ph2]
decomposed in hot methanol as indicated by the formation
of
RuCl2(CO)[η1-(P)-Ph2PCH2C(ϭO)tBu][η2-(P,O)-Ph2-
PCH2C(tBu)ϭO].[12] This latter complex was detected by
31P{1H} NMR spectroscopy.
Reversible and Irreversible Carbon Monoxide Binding by
Complexes 2؊2Ј
The 31P{1H} NMR spectrum of a solution of 2a (or 2b)
tion of the oxygen atom of the ketophosphane.[14] The in CD2Cl2 that was kept under carbon monoxide disclosed
31P{1H} NMR spectra (Table 1) consist of an AB spin sys- a new species, besides the minor presence of 2a (or 2b).
tem and the large coupling constant values (Ͼ 300 Hz) in- After removal of the carbon monoxide, recovery of pure 2a
dicate a mutual trans arrangement of the two phosphorus (or 2b) is indicated by the corresponding NMR spectrum.
nuclei.[15] The 1H and 13C{1H} NMR spectra both indicate The set of 31P{1H} NMR resonances corresponding to the
a plane of symmetry requiring a relative trans arrangement new species still consists of an AB spin system and large
of the two chloride ligands. Accordingly, the PCH2 protons coupling constant values (Ͼ 300 Hz), thus indicating a mu-
in complexes 2 and the PCMe2 methyl groups in complexes tual trans arrangement of the two phosphorus nuclei. At-
1
2Ј and 2ЈЈ are found to be equivalent by H NMR spectro- tempts to isolate the species failed, but such reversible car-
scopy. Furthermore, the two phenyl groups of the Ph2P bon monoxide binding by 2a (or 2b) is very similar to the
fragment are found to be equivalent by 13C{1H} NMR reversible formation of complexes III from complexes II, as
spectroscopy. The 13C NMR resonances assigned to the Cϭ depicted in Scheme 1. Therefore, the reversible formation of
O and CϵO carbon nuclei are close, but a simple compar- the all-trans derivatives (ttt)-RuCl2(CO)2(L)[η1-(P)-
ison between the 13C{1H} and 13C NMR spectra allows an Ph2PCH2C(ϭO)tBu] (3a,b) may be reasonably assumed
unambiguous determination, since only the keto resonance (Scheme 3). In contrast, an irreversible binding of carbon
1
is affected by far H-13C coupling.
monoxide by toluene solutions of complexes 2a,b and 2Јa
The thermal stability of complexes 2؊2ЈЈ depends on the occurs upon thermal activation (Ն 80 °C), yielding the col-
nature of the ancillary ligand L. The most stable complexes ourless cis,cis,trans derivatives (cct)-RuCl2(CO)2(L)[η1-(P)-
2348
Eur. J. Inorg. Chem. 2001, 2347Ϫ2359

New Octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] Complexes
FULL PAPER
Table 1. IR and 31P{1H} NMR data of the new complexes
IR[a]
31P{1H} NMR
δ(L)
Compound
ν(CϵO)
ν(CϭO) or (CϭCO)
δ(PO)
2JPP
(ttt)-RuCl2(CO)(L)[η2-(P,O)-ketophosphane)] complexes 2aϪe, 2Јa,e,f, 2ЈЈa
2a
1948, 1929
1939
1946, 1938
1941
1942
1936
1938
1965
1942
1635, 1624
1630
1633, 1627
1624
1620
1634
1637
1637
1673
45.3
48.5
49.0
49.4
45.1
65.1
65.1
64.0
38.2
5.6
356[b]
353[b]
343[c]
357[c]
389[c]
344[c]
374[b]
508[c]
347[c]
2b
19.8
41.9
33.0
131.8
4.5
131.6
128.4
2.5
2c
2d
2e
2Јa
2Јe
2Јf
2ЈЈa
(ttt)-RuCl2(CO)2(L)[η1-(P)-ketophosphane)] complexes 3a,b
3a
3b
10.9
13.5
Ϫ4.1
10.1
269[b]
272[b]
(cct)-RuCl2(CO)2(L)[η1-(P)-ketophosphane)] complexes 4a,b, 4Јa
4a
4b
4Јa
2056, 1988
2052, 1991
2045, 1992
1705
1694
1699
16.5
20.5
21.8
Ϫ2.2
13.4
1.0
339[c]
336[b]
346[c]
(cct)-RuCl2(CO)(MeCN)(L)[η1-(P)-ketophosphane)] complexes 5a,b,d
5a
5b
5d
1957
1950
1966
1702
1701
1708
23.7
26.5
27.5
Ϫ1.0
18.0
21.9
364[c]
359[c]
362[c]
(ccc)-RuCl2(CO)(L)[η2-(P,O)-ketophosphane)] complexes 6a,b, 6Јa
6a
6a, minor isomer in solution:
6b 1951
6b, minor isomer in solution:
6Јa 1960
1972
1624
1632
1620
52.7
63.8
49.6
60.9
74.2
23.1
16.8
38.3
34.5
21.3
31[c]
24[c]
28[b]
22[b]
30[b]
(ccc)-RuCl2(CO)2(L)[η1-(P)-ketophosphane)] complexes 7a,b
7a
7a, minor isomer in solution:
7b 2077, 1994
2078, 1988
1706
14.8
28.6
26.1
28.7
5.6
28[c]
29[c]
29[b]
28[b]
Ϫ9.7
12.4
3.4
1706
7b, minor isomer in solution:
Cationic derivatives 8a, 8Јa, 9a
8a
2081, 2018
2076, 2016
1987
1610
1622
1615
41.8
58.6
45.4
2.3
1.8
3.7
291[c]
285[c]
324[c]
8Јa
9a
(ttt)-RuCl(CO)2(L)[η2-(P,O)-enolatophosphane)] complexes 10a,c,e
10a
10c
10e
1989
1991
2006
1510
1498
1505
25.0
26.4
23.8
Ϫ3.8
36.0
123.8
222[c]
219[c]
255[c]
(ccc)-RuCl(CO)2(L)[η2-(P,O)-enolatophosphane)] complexes 11a,b
11a
11b
2070, 1968
2065, 1980
11b, minor isomer in solution:
1498
1500
47.0
46.6
42.6
Ϫ5.6
7.8
21.9
31[c]
31[c]
31[c]
(cct)-RuCl(CO)(LЈ)(L)[η2-(P,O)-enolatophosphane)] complexes 12a (LЈ ϭ CO), 13a (LЈ ϭ MeCN)
12a
13a
2034, 1977
1940
1505
1493
41.4
43.8
Ϫ1.1
0.8
302[c]
333[c]
[a]
[b]
[c]
ν in cmϪ1. Ϫ In CDCl3. Ϫ In CD2Cl2.
˜
ketophosphane] (4a,b and 4Јa) (Scheme 3). The formation tions (close to 2055 and 1990 cmϪ1) as expected for a relat-
of 4a,b and 4Јa involves an additional trans-to-cis re- ive cis arrangement of two carbonyl ligands, as well as an
arrangement of the chloride ligands, relative to the η2-(P,O) absorption close to 1700 cmϪ1 assigned to the uncoordin-
Ǟ η1-(P) transformation of the coordination of the keto- ated keto functionality. A relative cis arrangement of the
phosphane, therefore allowing the entrance of one carbon two carbonyl ligands obviously requires a relative cis ar-
monoxide molecule.
rangement of the two chlorine atoms.
The 31P{1H} NMR spectra of 4a,b still consist of an AB
spin system and the large coupling constant values (2JPP
Ͼ
Reversible Acetonitrile Binding by Complexes 2
300 Hz, Table 1) indicate the retention of the mutual trans
A trans-to-cis rearrangement of the chloride ligands is
1
arrangement of the two phosphorus nuclei. Both the H also involved when complexes 2a,b,d are heated under re-
and 13C{1H} NMR spectra of 4a,b and 4Јa indicate a plane flux in acetonitrile, yielding the lemon-yellow cis,cis,trans
of symmetry. Their IR spectra exhibit two strong absorp- complexes (cct)-RuCl2(CO)(NϵCMe)(L)[η1-(P)-ketophos-
Eur. J. Inorg. Chem. 2001, 2347Ϫ2359
2349

B. Demerseman
FULL PAPER
Isomerisation of Complexes 2؊2Ј
A slow reaction occurred when an orange solution of 2a
in toluene was heated at 80 °C under an inert gas, as indic-
ated by the formation of a pale-yellow precipitate. After
heating for 2 d and subsequent removal of the volatiles, the
1H and 31P{1H} NMR analysis of the resulting material
revealed a mixture consisting of a new species, 6a, as well
as unreacted 2a, in a 2:1 ratio (Scheme 5). It is worth noting
the thermal stability of complex 6a which was successfully
isolated in a 75% yield as an analytically pure precipitate
after a solution of 2a in toluene was heated under reflux.
Thus, this procedure was used to synthesize 6b starting
from 2b, while 6Јa was conveniently obtained after heating
2Јa in ethanol under reflux. The isomerisation of complexes
2a,b and 2Јa into complexes 6a,b and 6Јa also occurred
when solutions of 2a,b and 2Јa in dichloromethane were
exposed to sunlight. Similar treatment of a solution of 2a
or alternatively 6a, both led to mixtures of 2a and 6a in a
15:85 ratio, indicating a reversible process. This was deter-
Scheme 3
phane] (5a,b,d) (Scheme 4). The η2-(P,O) Ǟ η1-(P) modi-
fication of the coordination of the ketophosphane allows
one acetonitrile ligand to enter. The 31P{1H} NMR spectra
of complexes 5a,b,d exhibit large JPP coupling constant
values, indicating a retention of the relative trans arrange-
1
mined by H NMR spectroscopy. From the ratio it can be
2
seen that 6a is highly favoured. Irradiation from sunlight
proved useful in synthesising 6a and 6Јa, as detailed in the
Exp. Sect. Complexes 6a,b and 6Јa were characterised by
elemental analysis and spectroscopic studies. The 31P{1H}
1
ment of the phosphorus atoms. However, their H NMR
spectra show the two PCH2 protons of the ketophosphane
to be diastereotopic. Their 13C{1H} NMR spectra also in-
dicate a loss of symmetry. This lack of a plane of symmetry
suggests a relative cis arrangement of the two chloride li-
gands. Complexes 5a,b,d were found to be stable in the solid
state but not in dichloromethane solutions, as monitored by
1H and 31P{1H} NMR spectroscopy. Thus, after standing
for 1 d at room temperature, an NMR-spectroscopic sample
of pure 5a in CD2Cl2 shows a substantial presence of free
acetonitrile, as well as the recovery of 2a. The reaction of
acetonitrile with crude 2d (L ϭ PPh3), that was obtained as
an insoluble precipitate which retained several impurities,
allows the preparation of 5d as analytically pure yellow
crystals. Furthermore, a concentrated solution of 5d in
dichloromethane deposited orange crystals of pure 2d,
merely by standing for several days. A simple substitution
of the weakly bonded acetonitrile ligand by carbon monox-
ide (instead of the formation of 2a or 2d) was not observed
when a solution of 5a or 5d in dichloromethane was kept
under carbon monoxide. This result is likely to be related
to the kinetically favoured formation of trans derivatives in
such processes.[16]
2
NMR spectrum of 6Јa exhibits a small JPP coupling con-
stant value (Table 1), indicating a relative cis arrangement
of the phosphorus atoms.[15] The 1H NMR spectrum shows
two inequivalent PCMe2 methyl groups. IR spectroscopy
indicates the coordination of the keto functionality, and this
η2-(P,O) coordination of the ketophosphane obviously re-
quires a relative cis arrangement of the corresponding oxy-
gen and phosphorus coordinating atoms. Furthermore, the
13C{1H} NMR resonance assigned to the carbon monoxide
2
ligand in 6Јa discloses two small JPC coupling constant
values (2JPC ϭ 19.8 and 12.6 Hz), indicating a cis position
of the carbon monoxide ligand relative to both phosphorus
atoms. Therefore, only two octahedral structures, namely A
and B as depicted in Scheme 5, remain conceivable. The
NMR- and IR-spectroscopic study of 6a leads to the same
conclusion when some additional weak resonances are
omitted. These resonances are too weak to allow further
characterisation of the corresponding species; however,
2
31P{1H} NMR spectroscopy does show a small JPP coup-
ling constant value. The NMR-spectroscopic study of 6b
was more informative and shows the presence of two iso-
mers in a 3:2 ratio. These two isomers involve both a mutual
cis arrangement of the phosphorus atoms and a cis arrange-
ment of the carbon monoxide ligand relative to the phos-
phorus atoms, as expected for a mixture of A and B. To
summarise these results, complex 6Јa, which involves the
bulkiest ketophosphane 1Ј and a small ligand L ϭ PMe3,
shows only one isomer in solution, A or B. Complex 6b,
which involves the smaller ketophosphane 1 but a bulkier
ligand L ϭ PMePh2, shows a mixture of A and B isomers
in solution. Complex 6a, which involves the ketophosphane
1 and L ϭ PMe3, will also show a mixture of A and B
isomers, but one is highly favoured.
Scheme 4
2350
Eur. J. Inorg. Chem. 2001, 2347Ϫ2359

New Octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] Complexes
FULL PAPER
in a dichloromethane solution, but is converted into 4b on
dissolution in methanol, even at ambient temperature. The
straightforward formation of 4Јa on treatment of 6Јa with
carbon monoxide, is indicative of the steric effect of the
bulky ketophosphane 1Ј, favouring a cis-to-trans rearrange-
ment of phosphorus atoms.
Formation of Cationic Derivatives
Halide abstraction from 7a using silver tetrafluoroborate
creates an unsaturated centre that was found to trigger a
cis-to-trans rearrangement of phosphorus atoms. This pro-
duces the cationic derivative 8a in which the oxygen atom
from the ketophosphane ligand completes the coordination
at the ruthenium centre (Scheme 6). Complexes 4a and 4Јa
are also convenient precursors for the synthesis of such cat-
ionic derivatives, and afford the expected derivatives 8a and
8Јa, respectively, through the removal of a chloride ligand
(Scheme 6). In contrast, attempts to obtain cationic derivat-
ives starting from a complex 2, such as 2a, invariably failed,
even under carbon monoxide.
Scheme 5
Binding of Carbon Monoxide by Complexes 6؊6Ј
Dichloromethane solutions of 6a and 6b were found to
bind carbon monoxide (1 atm, ambient temperature) af-
fording 7a and 7b, respectively (Scheme 5). Complexes 6a
and 6b were recovered in the absence of carbon monoxide,
indicating a reversible reaction. It should be noted that this
process does not affect the A/B ratio (in 6a and 6b). In
contrast, 6Јa irreversibly adds carbon monoxide affording
the cct derivative 4Јa. This involves a cis-to-trans rearrange-
ment of the phosphorus atoms. The NMR spectra of both
7a and 7b show a mixture of two isomers, namely AЈ and
2
CЈ (Scheme 5). The small JPP coupling constant values
(Table 1) clearly indicate the retention of the cis arrange-
ment of the phosphorus atoms. The 1H NMR spectrum
shows the PCH2 protons of the ketophosphane 1 to be in-
equivalent and rules out a trans mutual arrangement of the
two chlorine atoms. The 13C{1H} NMR spectra indicate,
for each molecule AЈ and CЈ that one carbon monoxide
ligand is located in a cis position relative to the two phos-
phorus atoms and the second one in a trans PϪRuϪCO
arrangement.[15] Thus, only the two octahedral structures
AЈ and CЈ remain conceivable. The isomeric structures AЈ
and CЈ both show cis mutual arrangements of the two
chlorine atoms and of the two carbonyl ligands, respect-
ively, and are thus the two conceivable structures for an all-
cis-RuX2(CO)2(L)(LЈ) complex. It is interesting to note that
a simple substitution of the coordinated oxygen atom in A
by an entering carbon monoxide molecule will lead to AЈ.
Scheme 6
The structures of complexes 8a and 8Јa are unambigu-
However, a similar exchange of the coordinated oxygen ously deduced from their 31P{1H} NMR spectra, which ex-
2
atom in B by carbon monoxide will result in the formation hibit large JPP coupling constant values (Table 1) indicat-
of a symmetrical structure with trans carbon monoxide li- ing a trans arrangement of the phosphorus atoms, and from
gands, rather than CЈ. This is not experimentally detected. their IR spectra which indicate a cis arrangement of the
The stability of complexes 7a,b is related to the nature of carbonyl ligands and the coordination of the keto func-
the ancillary ligand L. Complex 7a (L ϭ PMe3) was found tionality. The observation of two inequivalent PCH2 pro-
1
to be stable in a dichloromethane solution, or alternatively tons by H NMR spectroscopy also suggests a relative cis
in a methanol solution, at ambient temperature and under arrangement of the two carbonyl ligands. The substitution
carbon monoxide, but is converted into 4a in hot methanol of one chloride ligand by the oxygen atom from the keto-
(see Exp. Sect.). In contrast, 7b (L ϭ PMePh2) is stable phosphane was also achieved starting from the fragile (pre-
Eur. J. Inorg. Chem. 2001, 2347Ϫ2359
2351

B. Demerseman
FULL PAPER
sumably owing to its labile acetonitrile ligand) complex 5a, isomers for 11b. These isomers involve both a relative cis
which reacts with silver tetrafluoroborate to yield the more arrangement of the phosphorus atoms and of the carbon
stable cationic derivative 9a (Scheme 6).
monoxide ligands, respectively. For each structure, one car-
bon monoxide ligand is located in a cis position relative
to the two phosphorus atoms, whereas the second carbon
monoxide ligand is located in a trans position relative to a
phosphorus atom, but three structures remain conceivable
(vide infra). The formation of the enolatophosphane deriv-
atives 12a and 13a, starting from the neutral cct isomer 4a
and from the cationic derivative 9a, respectively, formally
consists solely of the removal of one molecule of HCl or
H[PF6] (Scheme 7), and was also found to be very stereose-
lective. This was monitored by 31P{1H} NMR spectroscopy.
Stereoselective Synthesis of Enolatophosphane Derivatives
Complexes 2a,c,e were found to be rather robust under
basic conditions (K2CO3 in dichloromethane or KOH in
methanol). However, the consumption of the starting mat-
erial was detected by 31P{1H} NMR spectroscopy after pro-
longed reaction times (several days at ambient temper-
ature), but the observation of very numerous new reson-
ances indicated an intractable mixture. Under such basic
conditions and under carbon monoxide, a fast and selective
process occurred, resulting in the formation of the enolato-
phosphane complexes 10a,c,e. It is worth noting that the
complexes 10a,c,e retain an all-trans structure based on two
trans-coordinating phosphorus atoms, two trans-carbonyl
ligands and two trans-X-type coordinating atoms
(Scheme 7). The process formally consists of the removal of
one HCl molecule and the coordination of one molecule
of carbon monoxide. Derivatives 6a,b reacted in a similar
manner and afforded the enolatophosphane derivatives
11a,b, respectively, which retain a relative cis arrangement
of the phosphorus atoms. The NMR-spectroscopic study of
11a,b discloses one isomer for 11a, but a mixture of two
Discussion
The removal of the arene ligand from RuCl2(L)(η6-p-cy-
mene) complexes allows the coordination of a ketophos-
phane along with a CO ligand, thus providing access to a
new family of octahedral Ru complexes bearing two distinct
phosphorus-containing ligands. The process selectively
leads to all-trans complexes based on of two trans-chlorine
and trans-phosphorus atoms. The hemilabile character of
the ketophosphane ligand allows the reversible formation
of new all-trans-RuX2(CO)2L2-type complexes (but with
distinct L ligands) by reversible uptake of carbon monox-
ide. Previous studies concerning RuX2(CO)2L2 complexes
have proved that all-trans complexes easily rearrange under
thermal activation into their thermodynamically favoured
cct isomers through a preliminary cleavage of one RuϪCO
bond. The mechanism of this transformation has been thor-
oughly elucidated.[16] Therefore, the formation of complexes
of type 4 and 5 under thermal activation and in the pres-
ence of an entering ligand such as carbon monoxide or ace-
tonitrile might be expected, and this accounts for the recov-
ery of complexes of type 2 from 5 by loss of acetonitrile.
The behaviour of complexes 2 under thermal activation and
in the absence of an entering ligand was less predictable.
Whereas all-trans-RuX2(CO)2L2 complexes rearrange into
their cct isomers, complexes of type 2 selectively afford the
corresponding all-cis isomers 6. This observation suggests
that the formation of cct isomers of 2 (with cis-chlorine and
trans-phosphorus atoms) is disfavoured due to the require-
ment of
a (Cϭ)OǞRuϪCl trans arrangement (only
OǞRuϪCl cis arrangements are observed in complexes 2
and 6). In contrast, the coordination of carbon monoxide
is stabilised through the trans effect of a chloride ligand in
(cct)-RuX2(CO)2L2 complexes. As depicted in Scheme 8,
the transformation of complexes 2 into complexes 6 may be
assumed to involve a pentacoordinated intermediate arising
from the cleavage of the oxygenϪruthenium bond. Such a
Berry rearrangement[17] through a dissociative pathway al-
ready accounts for the isomerisation of all-trans-RuX2-
(CO)2L2 complexes into their all-cis isomers.[16]
Scheme 7
2352
Eur. J. Inorg. Chem. 2001, 2347Ϫ2359

New Octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] Complexes
FULL PAPER
Scheme 8. Rationale accounting for the reversible isomerisation of
complexes 2a,b and 2Јa into complexes 6a,b and 6Јa
The formation of complexes 6 preserves the hemilabile
property of the ketophosphane ligand as emphasised by the
reactivity of complexes 6 towards carbon monoxide. Com-
plexes 6a and 6b reversibly bind carbon monoxide to afford
7a and 7b, respectively. Solutions of 7a and 7b in dichloro-
methane both reveal a mixture of two all-cis isomers. As
depicted in Scheme 9, a comparison of the structures of
type 6 and 7 complexes excludes a mechanism based on
the CO displacement of the weakly bound oxygen atom in
Scheme 9. Comparison between the distinct structures of com-
plexes 6a,b, 7a,b, and 11a,b
complexes 6, despite the fact that the structure AЈ of 7 may of analogous dinuclear compounds by halogen-bridge
arise from A of 6. The structure CЈ which is also observed formation from RuX2(CO)2L2 complexes, which has been
in complexes 7, is unexpected when compared with A and previously reported,[15,16] further supports such a mechan-
B of complexes 6. The expected structure BЈ (Scheme 9) was ism.
not detected experimentally.
The formation of the enolatophosphane derivatives
Moreover, the AЈ/CЈ ratio in a complex of 7 is unambigu- 10a,c,e, 11a,b, and 12a (Scheme 7) was found to be highly
ously distinctly related to the A/B ratio in the parent com- stereoselective. Preliminary coordination of the entering li-
plex 6. Thus, the complete reversibility of the transforma- gand, subsequent deprotonation of the η1-(P)-coordinated
tion of 6 to 7 provides further evidence for a dynamic equi- ketophosphane and substitution of one chloride ligand by
librium between A and B, and between AЈ and CЈ. The fa- an anionic oxygen atom are the steps of a simple mechan-
cile recovery of 6a (or 6b) from 7a (or 7b) illustrates the ism which account for the stereoselective formation of
easy loss of carbon monoxide by 7. However, preliminary 10a,c,e and 11a,b. The formation of 12a starting from 4a,
cleavage of one RuϪCO bond in 7 (dissociative mechanism) in which the ketophosphane is already η1-(P)-coordinated,
will transiently generate a coordinatively unsaturated inter- clearly provides the experimental support to such a mech-
mediate favouring a cis-to-trans rearrangement of the phos- anism. The formation of 13a starting from the cationic
phorus atoms.[16] Therefore, an associative mechanism will complex 4a, involves the simple deprotonation of the keto-
more likely account for the retention of the all-cis geometry. phosphane ligand. The NMR-spectroscopic study of
The reversible A Ǟǟ B and AЈ Ǟǟ CЈ transformations are also 10a,c,e allows an unambiguous structural determination.
easy. They may formally involve the exchange of the posi- The structural determination is less accurate in the case of
tions of the chlorine atom and the oxygen atom for the A
11a,b, but only cis-phosphorus and cis-carbonyl arrange-
Ǟǟ B isomerisation, and of the chlorine atom and the carbon ments are observed. Thus, three structures, namely AЈЈ, DЈЈ,
monoxide ligand for the AЈ ǟǞ CЈ isomerisation. As depicted and CЈЈ (Scheme 9), remain conceivable after the examina-
in Scheme 10, all these reversible transformations may be tion of the NMR-spectroscopic data. Only one of them is
achieved without any involvement of coordinatively unsat- involved in the case of 11a, but two in the case of 11b which
urated species. Associative pathways consisting of the tran- reveals a mixture of two isomers. The AЈЈ and DЈЈ structures
sient formation of halogen-bridged dinuclear species easily show an OϪRuϪCO trans arrangement which may arise
account for the experimental observations. The formation from AЈ and CЈ in the corresponding parent compound 7.
Eur. J. Inorg. Chem. 2001, 2347Ϫ2359
2353

B. Demerseman
FULL PAPER
remarkably differ from RuX2(CO)2L2 compounds in which
the cct isomers are thermodynamically favoured. The cleav-
age of the OǞRu bond in complexes 2, that occurs under
thermal activation or sunlight irradiation, results in a true
coordinatively unsaturated species which allows the forma-
tion of stable cis-RuCl2(CO)(L)[η2-(P,O)-ketophosphane]
derivatives according to a Berry rearrangement. Under less
drastic conditions, the substitution of the coordinated oxy-
gen atom by an entering ligand such as carbon monoxide
probably occurs through an associative mechanism, al-
lowing the geometry to be retained. The easy deprotonation
of the ketophosphane Ph2PCH2C(ϭO)tBu allows the gen-
eration of RuCl(CO)2(L)[η2-(P,O)-enolatophosphane] de-
rivatives, and this transformation also preserves the geo-
metry of the corresponding precursor complexes.
Experimental Section
General: The reactions were performed using Schlenk-type tech-
niques, but only the handling of ketophosphanes required a rigor-
ous exclusion of oxygen. Solvents were distilled under an inert gas
after drying according to conventional methods. Ϫ Elemental ana-
lyses were performed by the Service de Microanalyse du CNRS,
Vernaison, France. Ϫ Infrared spectra were recorded with a Nicolet
205 FT infrared spectrometer as Nujol mulls. Ϫ NMR spectra were
recorded at 297 K with an AC 300 FT Bruker instrument (1H:
300.13; 13C: 75.47; 31P: 121.50 MHz; absolute values of coupling
constants in Hz) and referenced internally to the solvent peak. The
following abbreviations are used: s: singlet; d: doublet; t: triplet; ta:
apparent triplet; q4: quadruplet; m, unresolved multiplet. Ϫ The
precursor complexes RuCl2(L)(η6-p-cymene) were obtained by tre-
ating [RuCl2(η6-p-cymene)]2 with a stoichiometric amount of the
corresponding phosphorus derivative L.[18] The ketophosphanes
Scheme 10. Simple rationale accounting for the easy isomerisation
of complexes 6a,b and 7a,b
Only CЈ may lead to the third structure CЈЈ, which shows a
ClϪRuϪCO trans arrangement. It should be noted that a
chloride ligand is more labile when trans to a phosphorus
atom. Therefore, the CЈ Ǟ CЈЈ transformation will be a fa-
voured pathway and the observation of only one isomer
when starting from 7a will thus suggest the structure CЈЈ
for 11a. The precursor 7b involves a bulkier ancillary ligand
L ϭ PMePh2 than L ϭ PMe3 in 7a. For steric reasons, a
slower CЈ Ǟ CЈЈ transformation may result and a CЈ Ǟ DЈЈ
remains highly disfavoured, however, the AЈ Ǟ AЈЈ trans-
formation may become more competitive. This will result in
a mixture of the two isomers CЈЈ and AЈЈ in the case of 11b.
This behaviour emphasises the high stability of the
ClϪRuϪCO trans arrangement, and therefore also suggests
that the favoured isomer in complexes 6a,b and 6Јa is A.
The observation of isomer B is related to steric hindrance.
Ph2PCH2C(ϭO)tBu
(1),
Ph2PCMe2C(ϭO)iPr
(1Ј),
and
Ph2PCMe2CH2C(ϭO)Me (1ЈЈ), were prepared as previously re-
ported.[12,14]
Synthesis of Complexes 2؊2ЈЈ
(ttt)-RuCl2(CO)(PMe3)[Ph2PCH2C(tBu)؍O] (2a): RuCl2(PMe3)(p-
cymene) (13.3 g, 34.8 mmol) was added to a solution of ketophos-
phane 1 (9.90 g, 34.8 mmol) in methanol (200 mL). As for the pre-
paration of the other complexes 2؊2ЈЈ, the Schlenk tube was pro-
tected from light with aluminium foil and the mixture was then
stirred under carbon monoxide at room temperature. After 2 d, the
resulting slurry was heated and then filtered to obtain an orange
solution that deposited orange crystals on cooling. Yield 13.6 g,
70%. Ϫ 1H NMR (CDCl3): δ ϭ 7.60Ϫ7.39 (m, 10 H, Ph), 4.04 (dd,
2
4
2
2 H, JPH ϭ 10.1, JPH ϭ 1.4, PCH2), 1.70 (dd, 9 H, JPH ϭ 10.3,
4JPH ϭ 2.3, PMe3), 1.33 (s, 9 H, tBu). Ϫ 13C{1H} NMR (CD2Cl2):
δ ϭ 229.5 (dd, JPC ϭ 8.6, JPC ϭ 4.9, CϭO), 205.8 (dd, JPC
2
3
2
ϭ
Conclusion
3
17.1 and 11.0, CϵO), 133.6 (d, JPC ϭ 11.0, Ph2P, meta), 131.2
1
3
4
(dd, JPC ϭ 42.1, JPC ϭ 7.3, Ph2P, ipso), 131.0 (d, JPC ϭ 2.4,
Ph2P, para), 128.9 (d, 2JPC ϭ 9.8, Ph2P, ortho), 46.3 (d, 3JPC ϭ 3.5,
CMe3), 43.0 (d, 1JPC ϭ 23.8, PCH2), 27.1 (s, CMe3), 13.8 (d, 1JPC ϭ
28.9, PMe3). Ϫ 13C NMR (CD2Cl2, selected values): δ ϭ 229.5
This study of the new family of complexes trans-
RuCl2(CO)(L)[η2-(P,O)-ketophosphane] (2) emphasises the
stability of the OǞRu bond in
a trans-(C)ϭOǞ-
Ruǟ(CϵO) arrangement, and the inability of the oxygen
atom of the ketophosphane to coordinate trans to the chlor-
ide ligand. Due to this inability, the cct isomers of com-
plexes 2 remain the speculative species. From this point of
2
(broad, CϭO), 205.8 (dd, JPC ϭ 17.1 and 11.0, CϵO), 43.0 (td,
1JHC ϭ 131, JPC ϭ 23.8, PCH2), 13.8 (q4d, JHC ϭ 130, JPC
ϭ
1
1
1
28.9, PMe3). Ϫ C22H30Cl2O2P2Ru (560.4): calcd. C 47.15, H 5.40,
Cl 12.65, P 11.05; found C 47.48, H 5.49, Cl 12.60, P 11.00. Ϫ
view, RuCl2(CO)(L)[η2-(P,O)-ketophosphane] complexes Probably due to a solid-state effect, the IR absorptions (Table 1)
2354
Eur. J. Inorg. Chem. 2001, 2347Ϫ2359

New Octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] Complexes
FULL PAPER
assigned to the carbon monoxide ligand and to the keto func-
tionality are split.
ether. Yield 3.40 g, 52%. This crude product was found pure by
NMR-spectroscopic analysis. Fractional crystallisation from a
dichloromethane/ethanol mixture allowed the formation of orange-
yellow crystals of analytical quality. Ϫ 1H NMR (CD2Cl2): δ ϭ
(ttt)-RuCl2(CO)(PMePh2)[Ph2PCH2C(tBu)؍O] (2b):
A mixture
consisting of RuCl2(PMePh2)(p-cymene) (7.00 g, 13.8 mmol) and
ketophosphane 1 (4.00 g, 14.1 mmol) was dissolved in dichlorome-
thane (30 mL), and methanol (70 mL) was then added. The mixture
was stirred for 3 d (under carbon monoxide) and the resulting yel-
low slurry was concentrated under vacuum and diethyl ether was
then added. The yellow precipitate was collected by filtration and
then dissolved in dichloromethane (50 mL). The solution was fil-
tered and the orange filtrate was covered with ethanol (250 mL) in
an open flask allowing natural evaporation. Orange crystals were
2
4
7.93Ϫ7.40 (m, 20 H, Ph), 4.07 (dd, 2 H, JPH ϭ 10.5, JPH ϭ 1.5,
3
PCH2), 3.65 (d, 3 H, JPH ϭ 13.0, OMe), 0.99 (s, 9 H, tBu). Ϫ
C32H34Cl2O3P2Ru (700.5): calcd. C 54.86, H 4.89, Cl 10.12, P 8.84;
found C 54.59, H 4.87, Cl 10.30, P 8.50.
(ttt)-RuCl2(CO)(PMe3)[Ph2PCMe2C(iPr)؍O] (2Јa):
A mixture
consisting of RuCl2(PMe3)(p-cymene) (2.37 g, 6.20 mmol), keto-
phosphane 1Ј (1.85 g, 6.20 mmol) and methanol (40 mL), was
stirred for 2 d. The resulting yellow slurry was cooled to Ϫ20 °C
and the yellow crystalline precipitate was then collected by filtra-
tion and washed with cold methanol (20 mL). Yield 3.00 g, 84%.
Orange-yellow crystals were obtained by recrystallisation from hot
methanol. Ϫ 1H NMR (CD2Cl2): δ ϭ 7.61Ϫ7.40 (m, 10 H, Ph),
1
obtained. Yield 6.40 g, 68%. Ϫ H NMR (CDCl3): δ ϭ 7.82Ϫ7.36
(m, 20 H, Ph), 4.06 (dd, 2 H, 2JPH ϭ 10.5, 4JPH ϭ 1.3, PCH2), 2.23
2
4
(dd, 3 H, JPH ϭ 9.2, JPH ϭ 1.9, PMe), 1.08 (s, 9 H, tBu). Ϫ
C32H34Cl2O2P2Ru (684.5): calcd. C 56.15, H 5.01, Cl 10.36, P 9.05;
found C 56.18, H 4.92, Cl 10.31, P 9.06.
2
4
3.33 (m, 1 H, CHMe2), 1.67 (dd, 9 H, JPH ϭ 10.4, JPH ϭ 2.2,
3
3
PMe3), 1.54 (d, 6 H, JPH ϭ 9.9, PCMe2), 1.27 (d, 6 H, JHH
ϭ
(ttt)-RuCl2(CO)(PiPrPh2)[Ph2PCH2C(tBu)؍O]·CH2Cl2 (2c): Com-
plex 2c was similarly obtained in a 49% yield starting from
6.6, CHMe2). Ϫ 13C{1H} NMR (CD2Cl2): δ ϭ 229.8 (dd, JPC
ϭ
2
3
2
13.2, JPC ϭ 3.9, CϭO), 205.2 (dd, JPC ϭ 16.4 and 10.0, CϵO),
136.1 (dd, JPC ϭ 10.3, JPC ϭ 1.1, Ph2P, meta), 131.1 (d, JPC
2.3, Ph2P, para), 128.4 (dd, JPC ϭ 38.6, JPC ϭ 1.7, Ph2P, ipso),
128.1 (d, JPC ϭ 9.7, Ph2P, ortho), 55.3 (d, JPC ϭ 17.2, PCMe2),
RuCl2(PiPrPh2)(p-cymene) and ketophosphane 1. Ϫ 1H NMR
3
5
4
ϭ
2
(CD2Cl2): δ ϭ 7.69Ϫ7.30 (m, 20 H, Ph), 3.97 (dd, 2 H, JPH
ϭ
1
3
4
10.2, JPH ϭ 0.7, PCH2), 3.46 (m, 1 H, CHMe2), 1.04 (dd, 6 H,
2
1
3JHH ϭ 7.0, JPH ϭ 14.8, CHMe2), 0.87 (s, 9 H, tBu). Ϫ 13C{1H}
3
3
36.9 (d, JPC ϭ 2.9, CHMe2), 24.4 (s, PCMe2), 20.9 (s, CHMe2),
2
4
NMR (CD2Cl2): δ ϭ 228.0 (dd, JPC ϭ 7.1, JPC ϭ 4.6, CϭO),
206.8 (ta, JPC ഠ JPЈC ഠ 13.4, CϵO), 135.2 (d, JPC ϭ 8.2, Ph2P,
1
3
13.7 (dd, JPC ϭ 29.8, JPC ϭ 1.5, PMe3). Ϫ C23H32Cl2O2P2Ru
(574.4): calcd. C 48.09, H 5.62, Cl 12.34, P 10.78; found C 48.10,
H 5.63, Cl 12.11, P 10.93.
2
2
3
3
5
meta), 133.6 (dd, JPC ϭ 9.9, JPC ϭ 1.5, Ph2P, meta), 131.1 (d,
4JPC ϭ 2.1, Ph2P, para), 130.9 (dd, JPC ϭ 44.0, JPC ϭ 4.4, Ph2P,
1
3
4
1
ipso), 130.2 (d, JPC ϭ 1.7, Ph2P, para), 130.1 (dd, JPC ϭ 35.6,
(ttt)-RuCl2(CO)[P(OMe)Ph2][Ph2PCMe2C(iPr)؍O] (2Јe): A mix-
ture consisting of RuCl2[P(OMe)Ph2](p-cymene) (5.20 g,
9.95 mmol), ketophosphane 1Ј (3.08 g, 10.3 mmol), dichlorome-
thane (15 mL), and methanol (90 mL), was stirred for 4 d. The
resulting mixture was concentrated under vacuum and diethyl ether
was then added. A yellow precipitate (6.20 g) was collected by fil-
tration and washed with diethyl ether. This solid was dissolved in
dichloromethane (40 mL) and the orange solution was covered with
methanol (40 mL) and diethyl ether (100 mL) to obtain orange
3JPC ϭ 3.3, Ph2P, ipso), 128.8 (d, JPC ϭ 9.8, Ph2P, ortho), 128.1
2
2
3
(d, JPC ϭ 8.8, Ph2P, ortho), 45.9 (d, JPC ϭ 2.9, CMe3), 43.1 (d,
3
1JPC ϭ 24.2, PCH2), 26.8 (s, CMe3), 22.6 (dd, 1JPC ϭ 23.9, JPC
ϭ
1.8, CHMe2), 18.1 (s, CHMe2). Ϫ Easy loss of dichloromethane
from the crystals occurs as seen by the elemental analysis results,
which indicated the retention of only 0.8 CH2Cl2 per Ru;
C34H38Cl2O2P2Ru·(0.8 CH2Cl2) (712.6 ϩ 67.9 ϭ 780.5): calcd. C
53.55, H 5.11, Cl 16.35, P 7.94; found C 53.56, H 5.15, Cl 16.47,
P 7.95. Ϫ Probably due to a solid-state effect, the IR absorptions
(Table 1) assigned to the carbon monoxide ligand and to the keto
functionality are split.
1
crystals. Yield 5.15 g, 72%. Ϫ H NMR (CDCl3): δ ϭ 7.98Ϫ7.39
3
(m, 20 H, Ph), 3.63 (d, 3 H, JPH ϭ 12.9, OMe), 3.09 (m, 1 H,
3
3
CHMe2), 1.52 (d, 6 H, JPH ϭ 9.9, PCMe2), 0.80 (d, 6 H, JHH
ϭ
6.7, CHMe2). Ϫ C33H36Cl2O3P2Ru (714.6): calcd. C 55.47, H 5.08,
Cl 9.92, P 8.67; found C 55.38, H 5.06, Cl 10.12, P 8.47.
(ttt)-RuCl2(CO)(PPh3)[Ph2PCH2C(tBu)؍O]·2/3CH2Cl2 (2d):
A
mixture was prepared starting from RuCl2(PPh3)(p-cymene)
(9.50 g, 16.7 mmol), ketophosphane 1 (4.84 g, 17.0 mmol), dichlor-
omethane (25 mL), and methanol (130 mL). It was stirred for 3 d.
The resulting yellow precipitate was collected by filtration and
washed with diethyl ether (100 mL). Yield 9.70 g, 72%. The low
solubility of the compound precludes further purification.
(ttt)-RuCl2(CO)[P(OMe)3][Ph2PCMe2C(iPr)؍O] (2Јf): A solution
obtained from RuCl2[P(OMe)3](p-cymene) (4.66 g, 10.8 mmol), ke-
tophosphane 1Ј (3.23 g (10.8 mmol) and methanol (60 mL), was
stirred for 7 d. The resulting orange-yellow slurry was heated to
obtain an orange solution that was filtered. The filtrate was slowly
cooled to Ϫ20 °C to afford orange crystals. Yield 4.10 g, 61%. Ϫ
Recovery of 2d from 5d: A solution of 5d (4.00 g, 5.08 mmol) in
dichloromethane (50 mL) was kept in the dark at room temper-
ature. Orange crystals were collected after 10 d. Yield 1.58 g, 39%.
1H NMR (CD2Cl2): δ ϭ 7.59Ϫ7.38 (m, 10 H, Ph), 3.86 (d, 9 H,
3
3JPH ϭ 11.1, OMe), 3.34 (m, 1 H, CHMe2), 1.56 (d, 6 H, JPH
ϭ
10.1, PCMe2), 1.28 (d, 6 H, JHH ϭ 6.7, CHMe2). Ϫ 13C{1H}
NMR (CD2Cl2): δ ϭ 234.6 (dd, JPC ϭ 12.9, JPC ϭ 4.5, CϭO),
3
1
Ϫ H NMR (CD2Cl2): δ ϭ 7.75Ϫ7.35 (m, 25 H, Ph), 4.12 (dd, 2
2
3
2
4
H, JPH ϭ 10.7, JPH ϭ 1.4, PCH2), 1.11 (s, 9 H, tBu). Ϫ
C37H36Cl2O2P2Ru·(2/3 CH2Cl2) (746.6 ϩ 56.6 ϭ 803.2): calcd. C
56.32, H 4.69, Cl 14.71, P 7.71; found C 56.06, H 4.69, Cl 15.12,
P 7.33.
2
3
204.0 (dd, JPC ϭ 23.1 and 10.6, CϵO), 136.2 (dd, JPC ϭ 9.8,
5JPC ϭ 1.7, Ph2P, meta), 131.3 (d, JPC ϭ 1.9, Ph2P, para), 128.1
4
2
1
3
(d, JPC ϭ 9.9, Ph2P, ortho), 127.4 (dd, JPC ϭ 41.6, JPC ϭ 3.2,
Ph2P, ipso), 54.6 (d, JPC ϭ 18.0, PCMe2), 53.2 [d, JPC ϭ 3.8,
P(OMe)3], 36.9 (d, JPC ϭ 2.7, CHMe2), 24.5 (s, PCMe2), 20.8 (s,
1
2
(ttt)-RuCl2(CO)[P(OMe)Ph2][Ph2PCH2C(tBu)؍O] (2e): Methanol
3
(120 mL) was added to
a
solution consisting of
CHMe2). Ϫ C23H32Cl2O5P2Ru (622.4): calcd. C 44.38, H 5.18, Cl
11.39, P 9.95; found C 44.48, H 5.21, Cl 11.43, P 9.90.
RuCl2[Ph2PCH2C(ϭO)tBu](p-cymene)[14] (5.47 g, 9.26 mmol) and
P(OMe)Ph2 (3.20 mL, 16.0 mmol) in dichloromethane (60 mL).
This mixture was stirred for 3 d. The resulting yellow slurry was
concentrated under vacuum and diethyl ether was added. The yel-
(ttt)-RuCl2(CO)(PMe3)[Ph2PCMe2CH2C(Me)؍O] (2ЈЈa): Meth-
anol (80 mL) was added to a mixture of RuCl2(PMe3)(p-cymene)
low precipitate was collected by filtration and washed with diethyl (2.70 g, 7.06 mmol) and ketophosphane 1ЈЈ (2.65 g, 9.32 mmol),
Eur. J. Inorg. Chem. 2001, 2347Ϫ2359 2355

B. Demerseman
FULL PAPER
and this mixture was stirred for 2 d. The volatiles were evaporated
under vacuum. The resulting solid was dissolved in dichlorome-
stirred for 20 h under carbon monoxide, and the resulting colour-
less solution was concentrated to dryness under vacuum. Recrys-
thane (30 mL). The solution was filtered and methanol (50 mL) tallisation from hot methanol afforded colourless crystals. Yield
1
was added to the orange filtrate. The slow concentration of this
2.86 g, 86%. Ϫ H NMR (CD2Cl2): δ ϭ 7.87Ϫ7.28 (m, 10 H, Ph),
solution afforded orange crystals. Yield 2.35 g, 59%. Ϫ H NMR 3.38 (s, 3 H, MeOH), 3.26 (m, 1 H, CHMe2), 1.66 (dd, 9 H, 2JPH ϭ
1
(CD2Cl2): δ ϭ 7.84Ϫ7.30 (m, 10 H, Ph), 3.50 (d, 2 H, 3JPH ϭ 20.3,
10.9, JPH ϭ 2.4, PMe3), 1.47 (d, 6 H, JPH ϭ 12.9, PCMe2), 1.19
4
3
2
4
3
CH2), 2.50 (s, 3 H, MeCO), 1.57 (dd, 9 H, JPH ϭ 10.2, JPH
ϭ
(d, 6 H, JHH ϭ 6.7, CHMe2). Ϫ 13C{1H} NMR (CD2Cl2): δ ϭ
2.1, PMe3), 1.30 (d, 6 H, JPH ϭ 11.3, PCMe2). Ϫ 13C{1H} NMR
(CD2Cl2): δ ϭ 221.7 (s, CϭO), 205.7 (dd, JPC ϭ 16.5 and 13.0,
218.0 (s, CϭO), 193.9 (ta, JPC
ഠ
2JPЈC ഠ11.3, CϵO), 136.4 (d,
3
2
3JPC ϭ 7.9, Ph2P, meta), 132.8 (d, JPC ϭ 35.8, Ph2P, ipso), 130.5
2
1
CϵO), 135.8 (d, JPC ϭ 9.0, Ph2P, meta), 133.4 (d, JPC ϭ 38.8, (d, 4JPC ϭ 2.2, Ph2P, para), 127.8 (d, 2JPC ϭ 9.4, Ph2P, ortho), 53.2
3
1
4
2
1
3
Ph2P, ipso), 130.1 (d, JPC ϭ 2.2, Ph2P, para), 127.7 (d, JPC ϭ 9.3, (dd, JPC ϭ 17.2, JPC ϭ 2.3, PCMe2), 50.8 (s, MeOH), 35.7 (s,
2
1
Ph2P, ortho), 52.8 (d, JPC ϭ 6.4, CH2), 36.2 (s, MeCO), 30.3 (dd,
CHMe2), 22.0 (s, PCMe2), 20.7 (s, CHMe2), 15.3 (d, JPC ϭ 35.4,
1JPC ϭ 12.6, 3JPC ϭ 1.7, PCMe2), 25.6 (s, PCMe2), 13.2 (d, 1JPC ϭ PMe3). Ϫ C24H32Cl2O3P2Ru·MeOH (602.4 ϩ 32.0 ϭ 634.5): calcd.
28.8, PMe3). Ϫ C22H30Cl2O2P2Ru (560.4): calcd. C 47.15, H 5.40,
Cl 12.65, P 11.05; found C 47.35, H 5.38, Cl 12.84, P 11.00.
C 47.33, H 5.72, Cl 11.18, P 9.76; found C 47.26, H 5.85, Cl 10.93,
P 9.54.
Reactivity of Complexes 2 towards Acetonitrile
Reactivity of Complexes 2 towards Carbon Monoxide
(cct)-RuCl2(CO)(MeCN)(PMe3)[Ph2PCH2C(؍O)tBu] (5a): 2a
(1.96 g, 3.50 mmol) was heated in acetonitrile (25 mL) to obtain a
pale-yellow solution. On standing overnight at room temperature,
lemon-yellow crystals formed. They were collected and then
(ttt)-RuCl2(CO)2(PMe3)[Ph2PCH2C(؍O)tBu] (3a): A solution of
2a (0.15 g) in CDCl3 (2.0 mL) was stirred for 2 h under carbon
monoxide. The H NMR spectrum of the resulting solution shows
1
a 1:4 mixture of 2a and 3a, but the addition of hexane to such a
1
washed with acetonitrile (10 mL). Yield 1.75 g, 83%. Ϫ H NMR
1
solution selectively led to the recovery of 2a. Ϫ H NMR (CDCl3,
2
(CD2Cl2): δ ϭ 7.97Ϫ7.36 (m, 10 H, Ph), 4.40 (dd, 1 H, JHH
ϭ
available values for 3a from such a mixture of 2a and 3a): δ ϭ 4.04
2
2
2
17.1, JPH ϭ 8.6, PCH2, Ha), 4.25 (dd, 1 H, JHH ϭ 17.0, JPH
ϭ
2
4
2
(dd, 2 H, JPH ϭ 9.4, JPH ϭ 1.4, PCH2), 1.69 (dd, 9 H, JPH
ϭ
2
5.0, PCH2, Hb), 1.64 (s, 3 H, MeCN), 1.54 (dd, 9 H, JPH ϭ 10.3,
4
10.1, JPH ϭ 2.1, PMe3), 1.05 (s, 9 H, tBu).
4JPH ϭ 2.3, PMe3), 0.74 (s, 9 H, tBu). Ϫ 13C{1H} NMR (CD2Cl2):
2
4
2
δ ϭ 211.0 (dd, JPC ϭ 10.7, JPC ϭ 2.5, CϭO), 199.5 (dd, JPC
ϭ
(ttt)-RuCl2(CO)2(PMePh2)[Ph2PCH2C(؍O)tBu] (3b): A solution
3
13.6 and 11.5, CϵO), 135.2 (d, JPC ϭ 10.8, Ph, meta), 133.2 (d,
1
of 2b (0.15 g) in CDCl3 (2.0 mL) was treated similarly, and the H
3JPC ϭ 9.0, Ph, meta), 131.5 (d, JPC ϭ 38.6, Ph, ipso), 130.9 (d,
1
NMR spectrum of the resulting solution shows a ca. 1:1 mixture
of 2b and 3b. Ϫ 1H NMR (CDCl3, mixture of the two complexes):
δ ϭ 7.82Ϫ7.36 (m, 20 H, Ph), ca. 4.10 (2 H, PCH2), ca. 2.20 (m, 3
H, PMe), 1.08 and 1.05 (2 s, 9 H, tBu).
4JPC ϭ 2.7, Ph, para), 130.7 (d, JPC ϭ 38.6, Ph, ipso), 129.6 (d,
1
4JPC ϭ 1.8, Ph, para), 128.2 (d, JPC ϭ 9.9, Ph, ortho), 128.0 (d,
2
2JPC ϭ 9.0, Ph, ortho), 122.7 (s, MeCN), 45.9 (s, CMe3), 31.4 (d,
1JPC ϭ 19.9, PCH2), 25.8 (s, CMe3), 14.1 (d, JPC ϭ 30.5, PMe3),
1
3.6 (s, MeCN). Ϫ C24H33Cl2NO2P2Ru (601.5): calcd. C 47.93, H
5.53, Cl 11.79, N 2.33, P 10.30; found C 48.20, H 5.69, Cl 11.69,
N 2.45, P 10.33.
(cct)-RuCl2(CO)2(PMe3)[Ph2PCH2C(؍O)tBu] (4a): An orange so-
lution of 2a (1.00 g, 1.78 mmol) in hot toluene (80 °C, 40 mL) was
stirred for 2 d under carbon monoxide and the resulting colourless
solution was concentrated under vacuum to leave the crude prod-
uct. Recrystallisation from hot methanol afforded colourless crys-
tals of 4a. Yield 0.79 g, 75%. Ϫ 1H NMR (CD2Cl2): δ ϭ 7.78Ϫ7.34
(cct)-RuCl2(CO)(MeCN)(PMePh2)[Ph2PCH2C(؍O)tBu] (5b): Sim-
ilarly, 2b (2.12 g, 3.10 mmol) was heated in acetonitrile (30 mL) to
obtain a pale-yellow solution that deposited lemon-yellow crystals.
Yield 1.83 g, 81%. Ϫ 1H NMR (CD2Cl2): δ ϭ 8.00Ϫ7.32 (m, 20
2
(m, 10 H, Ph), 4.28 (d, 2 H, JPH ϭ 7.6, PCH2), 1.60 (dd, 9 H,
4
2JPH ϭ 10.8, JPH ϭ 2.4, PMe3), 0.76 (s, 9 H, tBu). Ϫ 13C{1H}
2
2
H, Ph), 4.48 (dd, 1 H, JHH ϭ 17.1, JPH ϭ 8.9, PCH2, Ha), 4.40
2
4
2
2
NMR (CD2Cl2): δ ϭ 210.0 (dd, JPC ϭ 10.0, JPC ϭ 1.9, CϭO),
(dd, 1 H, JHH ϭ 17.1, JPH ϭ 5.8, PCH2, Hb), 2.21 (dd, 3 H,
193.4 (dd, 2JPC ϭ 11.5 and 10.0, CϵO), 133.6 (d, 3JPC ϭ 9.8, Ph2P,
2JPH ϭ 9.9, JPH ϭ 1.7, PMe), 1.05 (s, 3 H, MeCN), 0.75 (s, 9 H,
4
1
3
tBu). Ϫ 13C{1H} NMR (CD2Cl2): δ ϭ 210.9 (dd, JPC ϭ 10.6,
2
meta), 131.2 (dd, JPC ϭ 44.9, JPC ϭ 1.4, Ph2P, ipso), 131.1 (d,
4JPC ϭ 2.3, Ph2P, para), 128.5 (d, JPC ϭ 10.0, Ph2P, ortho), 46.0
2
4JPC ϭ 1.7, CϭO), 199.8 (ta, JPC
ഠ
2JPЈC ഠ 12.5, CϵO),
2
1
(s, CMe3), 31.8 (d, JPC ϭ 25.0, PCH2), 26.0 (s, CMe3), 15.3 (dd,
135.6Ϫ127.8 (m, 4 Ph groups), 122.0 (s, MeCN), 46.0 (s, CMe3),
31.3 (d, 1JPC ϭ 21.3, PCH2), 25.8 (s, CMe3), 12.5 (dd, 1JPC ϭ 30.4,
3JPC ϭ 1.4, PMe), 2.7 (s, MeCN). Ϫ C34H37Cl2NO2P2Ru (725.6):
calcd. C 56.28, H 5.14, Cl 9.77, N 1.93, P 8.54; found C 56.16, H
5.18, Cl 9.76, N 2.12, P 8.25.
1JPC ϭ 33.3, JPC ϭ 1.2, PMe3). Ϫ 13C NMR (CD2Cl2, selected
3
1
1
values): δ ϭ 31.8 (td, JHC ϭ 130, JPC ϭ 25.0, PCH2). Ϫ
C23H30Cl2O3P2Ru (588.4): calcd. C 46.95, H 5.14, Cl 12.05, P
10.53; found C 46.63, H 5.33, Cl 11.83, P 10.16.
(cct)-RuCl2(CO)(MeCN)(PPh3)[Ph2PCH2C(؍O)tBu] (5d): Crude
2d (5.05 g, ഠ 6.29 mmol) was heated in a mixture of acetonitrile
(60 mL) and dichloromethane (15 mL) to obtain a pale-yellow so-
lution. On standing overnight at room temperature, lemon-yellow
crystals (3.23 g) were obtained. The concentration of the mother
liquor afforded a supplementary crop of crystals. Overall yield
(cct)-RuCl2(CO)2(PMePh2)[Ph2PCH2C(؍O)tBu]·CH2Cl2
(4b):
Complex 4b was similarly obtained as colourless crystals in a 70%
yield starting from 2b. Ϫ 1H NMR (CDCl3): δ ϭ 7.90Ϫ7.37 (m,
2
20 H, Ph), 4.50 (d, 2 H, JPH ϭ 8.0, PCH2), 2.30 (dd, 3 H, 2JPH
ϭ
10.6, 4JPH
ϭ
1.6, PMe), 0.79 (s,
9
H, tBu).
Ϫ
C33H34Cl2O3P2Ru·CH2Cl2 (712.6 ϩ 84.9 ϭ 797.5): calcd. C 51.21,
H 4.55, Cl 17.78, P 7.77; found C 51.21, H 4.64, Cl 16.98, P 7.71;
the low chlorine value is attributed to an easy partial loss of
CH2Cl2.
1
3.92 g, 79%. Ϫ H NMR (CD2Cl2): δ ϭ 8.03Ϫ7.33 (m, 25 H, Ph),
2
4.59 (dd, 1 H, 2JHH ϭ 17.0, JPH ϭ 8.4, PCH2, Ha), 4.52 (dd, 1 H,
2
2JHH ϭ 17.0, JPH ϭ 6.5, PCH2, Hb), 1.03 (s, 3 H, MeCN), 0.76
(s, 9 H, tBu). Ϫ C39H39Cl2NO2P2Ru (787.7): calcd. C 59.47, H
4.99, Cl 9.00, N 1.78, P 7.86; found C 59.54, H 4.97, Cl 9.24, N
1.83, P 7.67.
(cct)-RuCl2(CO)2(PMe3)[Ph2PCMe2C(؍O)iPr]·MeOH (4Јa): A so-
lution of 2Јa (3.00 g, 5.22 mmol) in hot toluene (85 °C, 60 mL) was
2356
Eur. J. Inorg. Chem. 2001, 2347Ϫ2359

New Octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] Complexes
Isomerisation of Complexes 2؊2Ј
FULL PAPER
was heated under reflux for 3 d. The resulting solution was concen-
trated to dryness to leave a pale-yellow solid that was identified as
pure 6Јa by NMR spectroscopy and elemental analysis. Ϫ 1H
NMR (CDCl3): δ ϭ 8.16Ϫ7.20 (m, 10 H, Ph), 3.28 (m, 1 H,
(ccc/ctc)-RuCl2(CO)(PMe3)[Ph2PCH2C(tBu)؍O] (6a). ؊ Photo-
Isomerisation of 2a: In a typical experiment, 2a (2.00 g, 3.57 mmol)
was dissolved in dichloromethane (50 mL) in a Schlenk flask. The
flask was closed and placed behind a window where it was exposed
to sunlight. After standing for two weeks (corresponding to ca.
50 h of exposure to sunlight ), the solvent was removed under va-
2
3
CHMe2), 1.52 (d, 9 H, JPH ϭ 11.0, PMe3), 1.49 (d, 3 H, JPH
ϭ
3
9.5, PCMe), 1.39 (d, 3 H, JPH ϭ 12.8, PCMe), 1.39 (d, 3 H,
3JHH ϭ 6.8, CHMe), 1.32 (d, 3 H, 3JHH ϭ 6.6, CHMe). Ϫ 13C{1H}
2
3
NMR (CD2Cl2): δ ϭ 232.4 (dd, JPC ϭ 7.2, JPC ϭ 1.8, CϭO),
1
cuum. The resulting solid was analysed by H NMR spectroscopy,
2
2
197.6 (dd, JPC ϭ 19.8 and 12.6, CϵO), 136.4 (d, JPC ϭ 9.0, Ph,
which indicated a 85% formation of 6a. The solid was then dis-
solved in hot ethanol (60 mL) to obtain a solution that deposited
pale-yellow crystals of 6a on cooling. Yield 1.35 g, 68%. Ϫ Ther-
mally Induced Isomerisation of 2a: A mixture of 2a (2.00 g,
3.57 mmol) and toluene (30 mL) was heated under reflux for 20 h.
The resulting cream-coloured precipitate was collected by filtration
and dried under vacuum. Yield 1.54 g, 77%. Ϫ 1H NMR (CD2Cl2):
1
3
ortho), 133.0 (d, JPC ϭ 46.7, Ph, ipso), 133.0 (d, JPC ϭ 9.0, Ph,
meta), 132.7 (s, Ph, para), 131.5 (s, Ph, para), 129.1 (d, 3JPC ϭ 10.8,
1
Ph, meta), 128.7 (d, 2JPC ϭ 10.8, Ph, ortho), 125.9 (d, JPC ϭ 43.1,
1
3
Ph, ipso), 58.6 (d, JPC ϭ 25.1, PCMe2), 37.1 (d, JPC ϭ 3.6,
CHMe2), 24.4 (s, CHMe), 23.0 (s, CHMe), 20.7 (s, PCMe), 20.5 (s,
1
PCMe), 18.8 (d, JPC ϭ 37.7, PMe3). Ϫ C23H32Cl2O2P2Ru: calcd.
C 48.09, H 5.62, Cl 12.34, P 10.78; found C 48.10, H 5.70, Cl 12.26,
P 10.67. Ϫ C23H32Cl2O2P2Ru·toluene (574.4 ϩ 92.1 ϭ 666.5):
calcd. C 54.06, H 6.05, Cl 10.64, P 9.29; found C 53.93, H 6.13, Cl
10.67, P 9.23.
2
2
δ ϭ 7.92Ϫ7.29 (m, 10 H, Ph), 4.26 (dd, 1 H, JHH ϭ 17.9, JPH
ϭ
2
2
11.4, PCH2, Ha), 4.09 (dd, 1 H, JHH ϭ 17.9, JPH ϭ 10.8, PCH2,
2
Hb), 1.51 (d, 9 H, JPH ϭ 11.2, PMe3), 1.29 (s, 9 H, tBu). Ϫ
13C{1H} NMR (CD2Cl2): δ ϭ 227.2 (ta, JPC
ഠ
3JPC ഠ 2.0, Cϭ
2
2
3
O), 197.5 (dd, JPC ϭ 19.5 and 12.8, CϵO), 134.4 (d, JPC ϭ 10.4, Reactivity of Complexes 6؊6Ј towards Carbon Monoxide
Ph, meta), 133.9 (d, JPC ϭ 50.1, Ph, ipso), 132.2 (d, JPC ϭ 2.4,
Ph, para), 131.7 (d, JPC ϭ 2.4, Ph, para), 131.2 (d, JPC ϭ 10.4,
Ph, ortho), 130.2 (d, JPC ϭ 24.4, Ph, ipso), 129.7 (d, JPC ϭ 9.8,
1
4
(ccc)-RuCl2(CO)2(PMe3)[Ph2PCH2C(؍O)tBu] (7a): A pale-yellow
solution of 6a (2.50 g, 4.46 mmol) in dichloromethane (30 mL) was
stirred for 20 h under carbon monoxide, and the resulting clear
solution was covered with hexane (100 mL) under the carbon mon-
oxide, to obtain 7a as colourless crystals. Yield 2.28 g, 87%. Altern-
atively, a solution of 6a (2.00 g, 3.57 mmol) in methanol (40 mL)
was stirred for 20 h under carbon monoxide to afford 7a (as deter-
mined by NMR and IR spectroscopy) as a white precipitate that
was collected by filtration and dried. Yield 1.73 g, 82%. Attempts
4
2
1
3
2
1
Ph, meta), 129.2 (d, JPC ϭ 11.0, Ph, ortho), 47.2 (d, JPC ϭ 30.5,
3
PCH2), 46.0 (ta, JPC
ഠ
4JPC ഠ 3.0, CMe3), 27.1 (s, CMe3), 19.2
(d, JPC ϭ 37.3, PMe3). The second but very minor isomer was
only detected by 31P{1H} NMR spectroscopy (Table 1).
1
Ϫ
C22H30Cl2O2P2Ru (560.4): calcd. C 47.15, H 5.40, Cl 12.65, P
11.05; found C 47.41, H 5.43, Cl 12.21, P 10.77.
(ccc/ctc)-RuCl2(CO)(PMePh2)[Ph2PCH2C(tBu)؍O] (6b). ؊ Photo-
Isomerisation of 2b: A solution of 2b (11.3 g, 16.5 mmol) in di- of the cct isomer 4a. Ϫ H NMR (CD2Cl2, asterisk-marked values
chloromethane (150 mL) was treated as above. After 3 weeks of for the major 3:1 isomer): δ ϭ 7.86Ϫ7.41 (m, 10 H, Ph), 4.72* and
exposure to sunlight, the solvents were evaporated and the re-
maining solid was dissolved in methanol (100 mL) to obtain a solu-
tion that slowly deposited pale-yellow crystals of 6b. Yield 5.95 g, Hb), 1.24* and 1.23 (2 d, 9 H, JPH ϭ 10.6* and 10.3, PMe3), 1.06
53%. The mother liquor was stirred under carbon monoxide for
20 h to afford a colourless precipitate of 4b (3.08 g, overall yield marked values for the major isomer): δ ϭ 209.9* (d, JPC ϭ 10.4,
79%, with respect to the recovery of ruthenium). Ϫ Thermally In-
to recrystallise from hot methanol afforded colourless crystals, but
1
2
2
4.33 (2 dd, 1 H, JHH ϭ 17.8* and 17.3, JPH ϭ 7.5* and 6.8,
PCH2, Ha), 4.39* and 4.02 (2 dd, 1 H, 2JPH ϭ 7.5* and 9.9, PCH2,
2
and 0.81* (2 s, 9 H, tBu). Ϫ 13C{1H} NMR (CD2Cl2, asterisk-
2
2
2
CϭO), 208.7 (d, JPC ϭ 6.1, CϭO), 194.9 (dd, JPC ϭ 15.9 and
2
duced Isomerisation of 2b: A mixture of 2b (3.54 g, 5.17 mmol) and 12.2, CϵO), 194.0* (ta, JPC
ഠ
2JPЈC ഠ 13.4, CϵO), 190.1* (dd,
toluene (50 mL) was heated as above to obtain a cream-coloured 2JPC ϭ 115.4 and 11.6, CϵO), 189.7 (dd, JPC ϭ 118.4 and 11.0,
2
precipitate. Yield 2.60 g, 73%. Ϫ 1H NMR (CD2Cl2, asterisk-
marked values for the major ca. 3:2 isomer): δ ϭ 7.90Ϫ7.60 (m, 20 3JPC ϭ 1.8, CMe3), 45.8 (d, JPC ϭ 2.4, CMe3), 36.4 (d, JPC
CϵO), 134.3Ϫ128.5 (m, Ph resonances for both isomers), 46.1* (d,
3
1
ϭ
2
1
H, Ph), 4.24* and 4.32 (2 dd, 1 H, JHH ϭ 17.9* and 18.0, 2JPH
ϭ
35.5, PCH2), 32.0* (d, JPC ϭ 28.5, PCH2), 26.7* (s, CMe3), 26.0
1
1
10.8* and 10.9, PCH2, Ha), 4.15 and 4.11* (2 dd, 1 H, partially
(s, CMe3), 18.9* (d, JPC ϭ 36.0, PMe3), 14.3 (d, JPC ϭ 33.0,
2
overlapped, JPH ϭ 10.8*, PCH2, Hb), 2.19* and 1.15 (2 d, 3 H, PMe3). Ϫ C23H30Cl2O3P2Ru (588.4): calcd. C 46.95, H 5.14, Cl
2JPH ϭ 10.9* and 9.5, PMe), 1.30* and 1.12 (2 s, 9 H, tBu). Ϫ
12.05, P 10.53; found C 46.80, H 5.12, Cl 11.91, P 10.73.
13C{1H} NMR (CDCl3, asterisk-marked values for the major iso-
(ccc)-RuCl2(CO)2(PMePh2)[Ph2PCH2C(؍O)tBu] (7b): Complex 7b
was studied by NMR spectroscopy after a solution of 6b in CDCl3
2
3
2
mer): δ ϭ 227.4* (ta, JPC ഠ JPЈC ഠ 1.7, CϭO), 227.2 (d, JPC
ϭ
2
2.9, CϭO), 203.9 (dd, JPC ϭ 19.1 and 14.5, CϵO), 197.4* (dd,
1
(or CD2Cl2) was stirred overnight under carbon monoxide. Ϫ H
2JPC ϭ 19.0 and 12.9, CϵO), 137.8Ϫ127.6 (m, Ph resonances for
NMR (CDCl3, asterisk-marked values for the major 4:1 isomer):
1
1
both isomers), 48.7* (d, JPC ϭ 31.5, PCH2), 48.5 (d, JPC ϭ 33.9,
PCH2), 45.6* (d, JPC ϭ 3.4, CMe3), 45.6 (d, JPC ϭ 2.9, CMe3),
2
δ ϭ 7.80Ϫ7.13 (m, 20 H, Ph), 4.88* and 4.47 (2 dd, 1 H, JHH
ϭ
3
3
18.0* and 17.4, 2JPH ϭ 6.2* and 4.8, PCH2, Ha), 4.35* and 1.98 (2
dd, 1 H, JPH ϭ 7.9* and 10.2, PCH2, Hb), 2.36 and 1.35* (2 d, 3
1
27.0* (s, CMe3), 26.7 (s, CMe3), 17.9* (d, JPC ϭ 36.1, PMe), 16.6
2
(d, 1JPC ϭ 37.0, PMe). Ϫ C32H34Cl2O2P2Ru (684.5): calcd. C 56.15,
2
H, JPH ϭ 10.9 and 10.5*, PMe), 0.82* and 0.71 (2 s, 9 H, tBu).
H 5.01, Cl 10.36, P 9.05; found C 55.86, H 5.10, Cl 10.40, P 9.29.
Ϫ
13C{1H} NMR (CDCl3, asterisk-marked values for the major
2
2
(ccc/ctc)-RuCl2(CO)(PMe3)[Ph2PCMe2C(iPr)؍O] (6Јa). ؊ Photo-
Isomerisation of 2Јa: Exposure to sunlight of a solution of 2Јa CϭO), 194.4* (ta, JPC ഠ JPЈC ഠ 12.4, CϵO), 193.6 (dd, JPC
isomer): δ ϭ 209.9* (d, JPC ϭ 10.6, CϭO), 208.2 (d, JPC ϭ 9.9,
2
2
2
ϭ
2
(3.00 g, 5.22 mmol) in dichloromethane (50 mL) resulted in a pale-
yellow solution. Toluene (150 mL) was then added and partial slow
evaporation of the solvents afforded pale-yellow crystals of
6Јa·toluene. Yield 2.36 g, 68%. Ϫ Thermally Induced Isomerisation
13.4 and 11.1, CϵO), 188.8 (dd, JPC ϭ 117.4 and 10.8, CϵO),
2
187.7* (dd, JPC ϭ 116.0 and 10.3, CϵO), 139.5Ϫ127.8 (m, Ph
resonances for both isomers), 45.8* (d, 3JPC ϭ 1.6, CMe3), 45.6 (d,
1
1
3JPC ϭ 1.3, CMe3), 32.3* (d, JPC ϭ 28.9, PCH2), 31.3 (d, JPC
ϭ
of 2Јa: A mixture of 2Јa (4.00 g, 6.96 mmol) and ethanol (60 mL) 26.8, PCH2), 26.0 (s, CMe3), 25.8* (s, CMe3), 11.9 (d, 1JPC ϭ 35.9,
Eur. J. Inorg. Chem. 2001, 2347Ϫ2359
2357

B. Demerseman
FULL PAPER
1
1
PMe), 11.6* (d, JPC ϭ 33.8, PMe). Ϫ The removal of the solvent 3JPC ϭ 3.2, CMe3), 43.0 (d, JPC ϭ 27.0, PCH2), 27.1 (s, CMe3),
1
3
from such solutions left a white solid consisting of a mixture of 7b
13.7 (dd, JPC ϭ 31.3, JPC ϭ 1.5, PMe3), 3.5 (s, MeCN). Ϫ
and 6b, but allowing the determination of the main IR absorptions C24H33BClF4NO2P2Ru (652.8): calcd. C 44.16, H 5.10, Cl 5.43, N
of 7b in the solid state (Table 1).
2.15, P 9.49; found C 43.93, H 5.25, Cl 5.12, N 2.08, P 9.37.
Enolatophosphane Complexes
Formation of 4b in Methanol: See synthesis of 6b.
(ttt)-RuCl(CO)2(PMe3)[Ph2PCH؍C(tBu)O] (10a): A mixture con-
sisting of 2a (3.00 g, 5.35 mmol) and K2CO3 (0.75 g, 5.43 mmol) in
dichloromethane (30 mL) was stirred for 2 d under carbon monox-
ide. The resulting mixture was filtered and the yellow filtrate was
concentrated leaving a crude product that was recrystallised from
a mixture of benzene (10 mL) and hexane (100 mL). Lemon-yellow
Reaction of 6Јa with Carbon Monoxide: A solution of 6Јa in dichlor-
omethane was stirred for 20 h under carbon monoxide and then
examined by 31P{1H} NMR spectroscopy which indicated a com-
plete conversion of 6Јa into 4Јa.
Cationic Derivatives
1
crystals were obtained. Yield 1.93 g, 65%. Ϫ H NMR (CD2Cl2):
(cct)-{RuCl(CO)2(PMe3)[Ph2PCH2C(tBu)؍O]}(BF4)·1/2CH2Cl2
(8a): A mixture consisting of 4a (3.50 g, 5.95 mmol) and AgBF4
(1.16 g, 5.95 mmol) in dichloromethane (60 mL) was stirred over-
night. The resulting solution was decanted, then filtered and the
filtrate was covered with diethyl ether (150 mL) to afford colourless
crystals. Yield 3.15 g, 78%. Complex 8a was obtained in a similar
manner when starting from 6a instead of 4a. Ϫ 1H NMR (CD2Cl2):
δ ϭ 7.84Ϫ7.33 (m, 10 H, Ph), 4.79 (ddd, 1 H, 2JHH ϭ 18.7, 2JPH ϭ
2
4
δ ϭ 7.87Ϫ7.37 (m, 10 H, Ph), 4.78 (dd, 1 H, JPH ϭ 2.7, JPH
ϭ
2
4
1.7, PCHϭ), 1.66 (dd, 9 H, JPH ϭ 9.9, JPH ϭ 1.9, PMe3), 1.11
(s, 9 H, tBu). Ϫ 13C{1H} NMR (CD2Cl2): δ ϭ 203.1 (dd, JPC
ϭ
2
3
2
16.4, JPC ϭ 5.2, ϭCO), 196.6 (ta, JPC
ഠ
2JPЈC ഠ 13.9, CϵO),
1
3
3
139.1 (dd, JPC ϭ 48.9, JPC ϭ 2.1, Ph, ipso), 131.5 (dd, JPC
10.5, JPC ϭ 1.6, Ph, meta), 130.0 (d, JPC ϭ 2.3, Ph, para), 128.7
(d, JPC ϭ 10.1, Ph, ortho), 71.7 (dd, JPC ϭ 61.5, JPC ϭ 1.8,
ϭ
5
4
2
1
3
3
PCHϭ), 39.7 (d, JPC ϭ 11.8, CMe3), 29.6 (s, CMe3), 15.6 (dd,
4
2
2
11.2, JPH ϭ 2.9, PCH2, Ha), 4.11 (dd, 1 H, JHH ϭ 18.7, JPH
ϭ
1JPC ϭ 29.4, 3JPC ϭ 1.6, PMe3). Ϫ C23H29ClO3P2Ru (552.0): calcd.
2
4
10.9, PCH2, Hb), 1.84 (dd, 9 H, JPH ϭ 11.3, JPH ϭ 2.6, PMe3),
C 50.05, H 5.30, Cl 6.42; found C 49.88, H 5.36, Cl 6.03.
1.36 (s, 9 H, tBu). Ϫ 13C{1H} NMR (CD2Cl2): δ ϭ 238.0 (ta,
2JPC ഠ JPЈC ഠ 4.9, CϭO), 195.5 (dd, 2JPC ϭ 13.3 and 9.0, CϵO),
3
(ttt)-RuCl(CO)2(PiPrPh2)[Ph2PCH؍C(tBu)O]·CH2Cl2 (10c):
A
2
3
190.0 (dd, JPC ϭ 11.6 and 9.2, CϵO), 134.4 (dd, JPC ϭ 11.7,
mixture consisting of 2c (1.41 g, 1.77 mmol) and K2CO3 (0.30 g,
2.17 mmol) in dichloromethane (25 mL), was stirred for 20 h under
carbon monoxide. The resulting mixture was filtered and the fil-
trate was covered with methanol to afford yellow crystals. Yield
5JPC ϭ 1.5, PhP, meta), 133.3 (d, JPC ϭ 2.6, PhP, para), 132.7 (d,
4
4JPC ϭ 2.3, PhP, para), 131.6 (d, JPC ϭ 47.7, PhP, ipso), 130.9 (d,
1
3JPC ϭ 11.4, PhP, meta), 130.4 (d, JPC ϭ 10.7, PhP, ortho), 130.0
2
2
1
3
1
(d, JPC ϭ 11.6, PhP, ortho), 125.2 (dd, JPC ϭ 53.5, JPC ϭ 2.6,
0.81 g, 65%. Ϫ H NMR (CD2Cl2): δ ϭ 7.83Ϫ7.27 (m, 20 H, Ph),
PhP, ipso), 47.9 (d, 3JPC ϭ 3.5, CMe3), 44.0 (d, 1JPC ϭ 30.5, PCH2),
2
4
4.69 (dd, 1 H, JPH ϭ 3.2, JPH ϭ 2.1, PCHϭ), 3.16 (m, 1 H,
1
3
3
3
27.0 (s, CMe3), 14.9 (dd, JPC ϭ 33.9, JPC ϭ 1.4, PMe3). Ϫ
C23H30BClF4O3P2Ru·1/2CH2Cl2 (639.7 ϩ 42.6 ϭ 682.2): calcd. C
41.37, H 4.58, Cl 10.39, P 9.08; found C 41.16, H 4.49, Cl 10.38,
P 9.22.
CHMe2), 1.10 (dd, 6 H, JHH ϭ 7.0, JPH ϭ 15.7, CHMe2), 1.01
(s, 9 H, tBu). Ϫ 13C{1H} NMR (CD2Cl2): δ ϭ 203.5 (dd, JPC
ϭ
2
4
2
15.7, JPC ϭ 5.2, ϭCO), 196.8 (dd, JPC ϭ 14.0 and 12.1, CϵO),
138.3 (dd, JPC ϭ 50.4, JPC ϭ 2.5, Ph2P, ipso), 134.2 (d, JPC
9.4, Ph2P, meta), 132.1 (dd, JPC ϭ 37.7, JPC ϭ 1.4, Ph2P, ipso),
1
3
3
ϭ
1
3
(cct)-{RuCl(CO)2(PMe3)[Ph2PCMe2C(iPr)؍O]}(BF4) (8Јa): Com-
plex 8Јa was obtained as colourless crystals in a 84% yield, as
above, starting from 4Јa. Ϫ 1H NMR (CD2Cl2): δ ϭ 7.94Ϫ7.20 (m,
3
5
4
131.5 (dd, JPC ϭ 10.0, JPC ϭ 1.2, Ph2P, meta), 130.6 (d, JPC
ϭ
1.8, Ph2P, para), 130.1 (d, 4JPC ϭ 2.4, Ph2P, para), 128.7 (d, 2JPC ϭ
2
10.5, Ph2P, ortho), 128.6 (d, JPC ϭ 9.1, Ph2P, ortho), 70.9 (d,
2
10 H, Ph), 3.47 (m, 1 H, CHMe2), 1.86 (dd, 9 H, JPH ϭ 11.3,
1JPC ϭ 62.7, PCHϭ), 39.5 (d, JPC ϭ 12.2, CMe3), 29.7 (s, CMe3),
3
3
4JPH ϭ 2.6, PMe3), 1.71 (d, 3 H, JPH ϭ 10.1, PCMe), 1.51 (d, 3
24.4 (d, JPC ϭ 22.6, CHMe2), 17.9 (s, CHMe2). Ϫ 13C NMR
1
H, 3JPH ϭ 12.9, PCMe), 1.41 (d, 3 H, 3JHH ϭ 6.8, CHMe), 1.23 (d,
3 H, 3JHH ϭ 6.6, CHMe). Ϫ C24H32BClF4O3P2Ru (653.8): calcd. C
44.09, H 4.93, Cl 5.42, P 9.48; found C 43.95, H 4.83, Cl 5.66,
P 9.60.
1
1
(CD2Cl2, selected values): δ ϭ 70.9 (dd, JHC ϭ 164, JPC ϭ 62.7,
PCHϭ). Ϫ C35H37ClO3P2Ru (704.1): calcd. C 59.70, H 5.30, Cl
5.03, P 8.80; found C 59.64, H 5.44, Cl 5.46, P 8.52.
(ttt)-RuCl(CO)2[P(OMe)Ph2][Ph2PCH؍C(tBu)O]·CH2Cl2 (10e): A
mixture consisting of 2e (4.14 g, 5.91 mmol) and K2CO3 (0.82 g,
5.93 mmol) in dichloromethane (60 mL), was stirred for 3 d under
carbon monoxide. The resulting mixture was filtered and the yellow
filtrate was concentrated leaving a yellow solid. Yield 3.20 g, 70%.
Yellow crystals were obtained after recrystallisation from dichloro-
(cct)-{RuCl(CO)(MeCN)(PMe3)[Ph2PCH2C(tBu)؍O]}(BF4) (9a):
Compound 5a (1.67 g, 2.78 mmol) was added to a cold mixture (Ϫ
60 °C) of AgBF4 (0.54 g, 2.78 mmol), dichloromethane (50 mL),
and acetonitrile (5 mL). After stirring overnight at room temper-
ature, the solvents were evaporated leaving a solid that was ex-
tracted with dichloromethane (20 mL). The solution was filtered
and the yellow filtrate was then covered with diethyl ether (100 mL)
1
methane/methanol. Ϫ H NMR (CD2Cl2): δ ϭ 7.83Ϫ7.30 (m, 20
2
H, Ph), 4.72 (ta, 1 H, JPH
ഠ
4JPH ഠ 2.6, PCHϭ), 3.63 (d, 3 H,
to afford lemon-yellow crystals. Yield 1.58 g, 87%. Ϫ 1H NMR
3JPH ϭ 13.3, OMe), 1.04 (s, 9 H, tBu). Ϫ C33H33ClO4P2Ru·CH2Cl2
(692.1 ϩ 84.9 ϭ 777.0): calcd. C 52.56, H 4.54, Cl 13.69, P 7.97;
found C 52.16, H 4.61, Cl 12.46, P 7.92; the low chlorine value is
likely to be due to to the easy loss of dichloromethane.
2
(CD2Cl2): δ ϭ 7.88Ϫ7.23 (m, 10 H, Ph), 4.62 (ddd, 1 H, JHH
ϭ
2
4
2
18.4, JPH ϭ 11.0, JPH ϭ 2.9, PCH2, Ha), 3.82 (dd, 1 H, JHH
ϭ
2
5
5
18.4, JPH ϭ 10.2, PCH2, Hb), 1.82 (ta, 3 H, JPH ഠ JPЈH ഠ 0.8,
MeCN), 1.69 (dd, 9 H, JPH ϭ 10.7, JPH ϭ 2.5, PMe3), 1.38 (s, 9
2
4
H, tBu). Ϫ 13C{1H} NMR (CD2Cl2): δ ϭ 234.7 (dd, JPC ϭ 7.0, (ccc)-RuCl(CO)2(PMe3)[Ph2PCH؍C(tBu)O] (11a): A mixture con-
sisting of 6a (3.43 g, 6.12 mmol) and K2CO3 (0.85 g, 6.15 mmol) in
(dd, JPC ϭ 12.0, JPC ϭ 1.8, Ph, meta), 132.8 (d, JPC ϭ 2.5, Ph, dichloromethane (40 mL), was stirred for 20 h under carbon mon-
2
2
3JPC ϭ 4.6, CϭO), 201.9 (dd, JPC ϭ 14.8 and 9.8, CϵO), 135.0
3
5
4
4
3
para), 131.5 (d, JPC ϭ 1.9, Ph, para), 131.1 (d, JPC ϭ 10.8, Ph, oxide. The resulting slurry was filtered and the filtrate was covered
1
3
meta), 130.4 (dd, JPC ϭ 41.4, JPC ϭ 1.5, Ph, ipso), 130.0 (d, with toluene (30 mL) and then hexane (100 mL), to afford pale-
1
2JPC ϭ 10.0, Ph, ortho), 129.7 (d, 2JPC ϭ 10.9, Ph, ortho), 122.4 (s,
yellow (almost colourless) crystals. Yield 2.86 g, 85%. Ϫ H NMR
1
3
2
MeCN), 127.0 (dd, JPC ϭ 49.7, JPC ϭ 2.3, Ph, ipso), 47.3 (d,
(CD2Cl2): δ ϭ 7.73Ϫ7.33 (m, 10 H, Ph), 4.74 (d, 1 H, JPH ϭ 4.4,
2358
Eur. J. Inorg. Chem. 2001, 2347Ϫ2359

New Octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] Complexes
FULL PAPER
2
PCHϭ), 1.27 (s, 9 H, tBu), 1.06 (d, 9 H, JPH ϭ 10.4, PMe3). Ϫ
C23H29ClO3P2Ru (552.0): calcd. C 50.05, H 5.30, Cl 6.42, P 11.22;
13C{1H} NMR (CD2Cl2): δ ϭ 201.7 (d, JPC ϭ 14.4, ϭCO), 199.4 found C 49.98, H 5.31, Cl 6.34, P 10.77.
(dd, JPC ϭ 14.4 and 10.8, CϵO), 189.3 (dd, JPC ϭ 113.1 and
10.8, CϵO), 141.1 (dd, JPC ϭ 58.8, JPC ϭ 2.2, Ph, ipso), 136.4
(dd, JPC ϭ 56.1, JPC ϭ 3.6, Ph, ipso), 131.5 (d, JPC ϭ 9.9, Ph,
2
2
2
(cct)-RuCl(CO)(MeCN)(PMe3)[Ph2PCH؍C(tBu)O] (13a): A mix-
ture consisting of 9a (1.00 g, 1.53 mmol) and K2CO3 (0.26 g,
1.90 mmol) in dichloromethane (25 mL), was stirred for 6 d and
then concentrated to dryness. The remaining solid was extracted
with toluene (15 mL). The solution was filtered and acetonitrile
(1.0 mL) was added to the filtrate that was then covered with hex-
ane (100 mL) to afford pale-yellow crystals. Yield 0.44 g, 50%. Ϫ
1H NMR (CD2Cl2): δ ϭ 7.80Ϫ7.29 (m, 10 H, Ph), 4.52 (dd, 1 H,
2JPH ϭ 3.3, 4JPH ϭ 1.1, PCHϭ), 1.58 (ta, 3 H, 5JPH ഠ 5JPЈH ഠ 0.9,
1
3
1
3
3
4
2
meta), 131.1 (d, JPC ϭ 2.7, Ph, para), 130.3 (d, JPC ϭ 10.8, Ph,
ortho), 130.3 (part of d, Ph, para), 129.6 (d, 3JPC ϭ 10.8, Ph, meta),
2
1
129.1 (d, JPC ϭ 10.8, Ph, ortho), 69.5 (d, JPC ϭ 64.6, PCHϭ),
3
1
39.9 (d, JPC ϭ 12.6, CMe3), 29.7 (s, CMe3), 13.3 (d, JPC ϭ 31.4,
PMe3). Ϫ 13C NMR (CD2Cl2, selected values): δ ϭ 69.5 (dd,
1JHC ϭ 164, JPC ϭ 64.6, PCHϭ). Ϫ C23H29ClO3P2Ru (552.0):
1
calcd. C 50.05, H 5.30, Cl 6.42, P 11.22; found C 50.02, H 5.42, Cl
6.36, P 11.28.
2
4
MeCN), 1.53 (dd, 9 H, JPH ϭ 9.9, JPH ϭ 2.1, PMe3), 1.21 (s, 9
H, tBu). Ϫ C24H32ClNO2P2Ru (565.0): calcd. C 51.02, H 5.71, Cl
6.27, N 2.48, P 10.96; found C 51.03, H 5.78, Cl 6.14, N 2.49,
P 10.84.
(ccc)-RuCl(CO)2(PMePh2)[Ph2PCH؍C(tBu)O] (11b): A mixture
consisting of 6b (2.04 g, 2.98 mmol) and K2CO3 (0.45 g,
3.26 mmol) in dichloromethane (40 mL), was stirred for 20 h under
carbon monoxide. The resulting slurry was filtered and the filtrate
was concentrated to dryness. The resulting solid was dissolved in a
hot mixture of toluene (30 mL) and dichloromethane (15 mL) to
obtain a clear solution that was covered with hexane (130 mL).
Colourless crystals were obtained. Yield 1.69 g, 84%. Ϫ H NMR
(CD2Cl2, asterisk-marked values for the major 9:1 isomer): δ ϭ
7.55Ϫ7.28 (m, 20 H, Ph), 4.89* and 4.84 (2 d, 1 H, JPH ϭ 4.4*
and 2.0, PCHϭ), 1.38* and 1.35 (2 s, 9 H, tBu), 1.22 and 1.20* (2
Acknowledgments
This work was supported by the ‘‘Centre National de la Recherche
´
Scientifique’’. The author is grateful to J.-P. Guegan for NMR-
technical assistance.
1
[1]
J. C. Jeffrey, T. B. Rauchfuss, Inorg. Chem. 1979, 18,
2
2658Ϫ2666.
[2]
A. Bader, E. Lindner, Coord. Chem. Rev. 1991, 108, 27Ϫ110.
[3]
E. Lindner, S. Pautz, M. Haustein, Coord. Chem. Rev. 1996,
2
4
dd, 3 H, JPH ϭ 10.7 and 9.5*, JPH ϭ 1.2 and 0.9*, PMe). Ϫ
155, 145Ϫ162.
13C{1H} NMR (CD2Cl2, asterisk-marked values for the major iso-
[4]
E. Lindner, A. Möckel, H. A. Mayer, H. Kühbauch, R. Fawzi,
mer): δ ϭ 201.8* (d, JPC ϭ 14.5, ϭCO), 199.4 (d, 2JPC ϭ 17.4, ϭ
2
M. Steimann, Inorg. Chem. 1993, 32, 1266Ϫ1271.
E. Lindner, A. Möckel, H.A. Mayer, R. Fawzi, Chem. Ber.
2
2
[5]
CO), 199.5 (dd, JPC ϭ 13.7 and 10.7, CϵO), 198.5* (dd, JPC
12.6 and 11.1, CϵO), 190.9 (dd, JPC ϭ 105.3 and 11.4, CϵO),
189.4* (dd, JPC ϭ 114.1 and 11.4, CϵO), 141.5Ϫ127.9 (m, Ph
resonances for both isomers), 70.6* (d, JPC ϭ 64.9, PCHϭ), 68.5
ϭ
2
1992, 125, 1363Ϫ1367.
[6]
2
E. Lindner, A. Möckel, Z. Naturforsch., Teil B 1992, 47,
1
693Ϫ696.
[7]
1
3
E. Lindner, B. Karle, Chem. Ber. 1990, 123, 1469Ϫ1473.
E. Lindner, U. Schober, R. Fawzi, W. Hiller, U. Englert, P.
(d, JPC ϭ 61.8, PCHϭ), 40.2* (d, JPC ϭ 12.2, CMe3), 39.7 (d,
[8]
3JPC ϭ 12.2, CMe3), 29.9 (s, CMe3 for both isomers), 11.6 (dd,
Wegner, Chem. Ber. 1987, 120, 1621Ϫ1628.
P. Braunstein, D. Matt, D. Nobel, S.-E. Bouaoud, B. Carluer,
1JPC ϭ 23.0, JPC ϭ 1.5, PMe), 11.2* (d, JPC ϭ 28.2, JPC ϭ 2.3,
PMe). Ϫ C33H33ClO3P2Ru (676.1): calcd. C 58.63, H 4.92, Cl 5.24,
P 9.16; found C 58.35, H 4.98, Cl 5.42, P 9.33.
3
1
3
[9]
D. Grandjean, P. Lemoine, J. Chem. Soc., Dalton Trans. 1986,
415Ϫ419.
[10]
P. Braunstein, D. Matt, Y. Dusausoy, Inorg. Chem. 1983, 22,
2043Ϫ2047.
H. Werner, A. Stark, M. Schulz, J. Wolf, Organometallics 1992,
11, 1126Ϫ1130.
(cct)-RuCl(CO)2(PMe3)[Ph2PCH؍C(tBu)O] (12a): A mixture con-
sisting of 4a (1.50 g, 2.20 mmol) and K2CO3 (0.31 g, 2.24 mmol) in
dichloromethane (20 mL), was stirred for 7 d as required to com-
plete the reaction, and then concentrated to dryness. The remaining
solid was extracted with toluene (25 mL). The solution was filtered
and the filtrate was covered with hexane (100 mL) to afford colour-
[11]
[12]
B. Demerseman, R. Le Lagadec, B. Guilbert, C. Renouard, P.
Crochet, P. H. Dixneuf, Organometallics 1994, 13, 2269Ϫ2283.
P. Braunstein, Y. Chauvin, J. Nähring, Y. Dusausoy, D. Bayeul,
[13]
A. Tiripicchio, F. Ugozzoli, J. Chem. Soc., Dalton Trans.
1995, 851Ϫ862.
B. Demerseman, B. Guilbert, C. Renouard, M. Gonzalez, P.
less crystals. Yield 0.90 g, 74%. Ϫ 1H NMR (CD2Cl2): δ ϭ
7.70Ϫ7.35 (m, 10 H, Ph), 4.58 (ta, 1 H, JPH
2
ഠ
4JPH ഠ 3.0,
[14]
2
4
PCHϭ), 1.66 (dd, 9 H, JPH ϭ 10.6, JPH ϭ 2.1, PMe3), 1.20 (s, 9
H. Dixneuf, D. Masi, C. Mealli, Organometallics 1993, 12,
H, tBu). Ϫ 13C{1H} NMR (CD2Cl2): δ ϭ 200.6 (dd, JPC ϭ 18.0,
2
3906Ϫ3917.
[15]
3JPC ϭ 7.2, ϭCO), 198.2 (dd, JPC ϭ 11.2 and 8.5, CϵO), 193.9
2
D. W. Krassowski, J. H. Nelson, K. R. Brower, D. Hauenstein,
R. A. Jacobson, Inorg. Chem. 1988, 27, 4294Ϫ4307.
C. F. J. Barnard, J. A. Daniels, J. Jeffery, R. J. Mawby, J. Chem.
2
2
1
(ta, JPC ഠ JPЈC ഠ 11.2, CϵO), 138.7 (d, JPC ϭ 51.2, Ph, ipso),
[16]
1
3
3
133.6 (dd, JPC ϭ 44.0, JPC ϭ 3.6, Ph, ipso), 133.2 (dd, JPC
ϭ
Soc., Dalton Trans. 1976, 953Ϫ961.
9.9, JPC ϭ 1.8, Ph, meta), 131.5 (dd, 3JPC ϭ 10.8, JPC ϭ 1.8, Ph,
5
5
[17]
R. S. Berry, J. Chem. Phys. 1960, 32, 933Ϫ938.
4
4
meta), 130.1 (d, JPC ϭ 2.7, Ph, para), 130.0 (d, JPC ϭ 2.7, Ph,
para), 128.9 (d, JPC ϭ 9.9, Ph, ortho), 128.4 (d, JPC ϭ 10.8, Ph,
ortho), 69.8 (dd, JPC ϭ 61.0, JPC ϭ 1.8, PCHϭ), 39.5 (d, JPC
12.6, CMe3), 29.8 (s, CMe3), 14.8 (d, JPC ϭ 30.4, PMe3). Ϫ
[18]
H. Le Bozec, D. Touchard, P. H. Dixneuf, Adv. Organomet.
2
2
Chem. 1989, 29, 163Ϫ247.
Received March 2, 2001
[I01077]
1
3
3
ϭ
1
Eur. J. Inorg. Chem. 2001, 2347Ϫ2359
2359