Synthesis and characterization of new ruthenium(II) complexes containing diisopropylmethylphosphine

Article abstract of DOI:10.1039/a902065i

The reaction between RuCl₃ and PⁱPr₂Me in 2-methoxyethanol yielded the five-co-ordinate complex [RuCl₂(CO)-(PⁱPr₂Me)₂] in which the phosphine groups show a cisoid arrangement. Th

Full text of DOI:10.1039/a902065i

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Synthesis and characterization of new ruthenium(II) complexes
containing diisopropylmethylphosphine
Emilio Bustelo, Manuel Jiménez-Tenorio, Ma Carmen Puerta* and Pedro Valerga
Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica,
Facultad de Ciencias, Universidad de Cádiz, Aptdo. 40, 11510 Puerto Real, Cádiz, Spain.
E-mail: carmen.puerta@uca.es
Received 16th March 1999, Accepted 1st June 1999
The reaction between RuCl3 and PiPr2Me in 2-methoxyethanol yielded the five-co-ordinate complex [RuCl2(CO)-
(PiPr2Me)2] in which the phosphine groups show a cisoid arrangement. The co-ordination sphere of the ruthenium
nucleus can be completed with neutral ligands such as CO, tBuNC, Hpz, 3,5-dimethylpyrazole and HN᎐CPh .
᎐
2
Likewise, it reacts with S-donor reagents like PhSH and 2-sulfanylpyridine and readily undergoes metathesis
reactions with salts of some chelating ligands like NaS2CNEt2, KS2COR (R = Me, Et or iPr) and K(acac)
which are bonded in a bidentate mode.
a new 16-electron complex containing diisopropylmethylphos-
Introduction
phine. On the basis of analogous reactions with different phos-
phines6 we attempted to obtain a good starting material with
the new phosphine and were first interested in the possibility of
synthesis of the hypothetical transoid complex [RuH(Cl)(CO)-
(PiPr2Me)2]. However, the interaction of ruthenium trichloride
in 2-methoxyethanol with three equivalents of the phosphine
PiPr2Me, heated under reflux for 24 h, yields the unexpected but
also unsaturated complex [RuCl2(CO)(PiPr2Me)2] 1 instead of
the hydridochloride compound, as a yellow solid with a yield
of 70–90%. This complex shows a cisoid arrangement between
the phosphine ligands, displaying two doublet resonances in the
31P-{1H} NMR spectrum with a P–PЈ coupling constant of 23.2
Hz. No fluxional processes have been observed at high or low
temperatures. The arrangement of the phosphines and the
impossibility of giving rise to the hydride formation are the
main structural differences with analogous complexes with the
related ligands PiPr3 and PtBu2Me, both bulkier and probably
stronger donors.
The interest in the synthesis and characterization of new co-
ordinatively unsaturated transition-metal complexes arises
because they represent very reactive intermediates in many
catalytically operating processes1,2 and provide transition-metal
sites for the binding and activation of small molecules.3 The use
of innovative auxiliary ligands gives rise to new complexes
related to others previously known but with the possibility of
new features and new ways to the understanding of these sort
of processes.4 Bulky phosphine ligands are one of the most
commonly employed. They are implicated in many different
processes of co-ordination and catalytic chemistry,2 and a small
steric modification of a phosphine ligand can dramatically alter
the reactivity of a complex.5 In this context, a family of five-co-
ordinate complexes of general formula [MH(Cl)(CO)(PR3)2]
have been the subject of extensive analysis. The bulkiness and
the donating power of the phosphine are decisive in hydride
formation and in the stabilization of co-ordinatively unsatur-
ated species. Phosphine ligands like PCy3, PiPr3 or PtBu2R
(R = Me or Et) are able to stabilize 16-electron complexes
from RuCl3 in primary alcohols.6 A considerable part of these
investigations has grown up around the complexes [MH(Cl)-
(CO)(PiPr3)2] (M = Ru or Os) and their derivatives,7 which have
exhibited a rich chemistry and catalytic activity.1 However, sat-
urated compounds like [RuH(Cl)(CO)(PPh3)3] are frequently
employed as starting materials and catalysts.8 The complex
[RuCl2(CO)2(PEt3)2] was used in the synthesis of a series of
ruthenium() bis(acetylides) and bis(diacetylides).9 Similar
complexes with triisopropylstibine have recently been obtained,
also using RuCl3, affording the saturated but reactive com-
pounds [RuCl2(CO)(SbiPr3)3] and [RuH(Cl)(CO)(SbiPr3)3].4
We have used diisopropylmethylphosphine as a new ligand in
the synthesis of new organometallic complexes. In addition to
its own electronic and steric characteristics, this phosphine may,
similarly to PtBu2Me, respond to the steric demands involved
during reactions like adduct formation.5a We are interested in
the synthesis of new unsaturated complexes and their reactivity
towards mono- and bi-dentate ligands, potentially N-, C-,
O- and S-donors.
The lack of suitable crystals of compound 1 for X-ray dif-
fraction prevents us from determining whether this complex is
trigonal bipyramidal or square pyramidal. However, the pro-
posed structures for species like [RuH(Cl)(CO)L2] (L = PiPr3,6a
PtBu2Me6b or Cy6c), [RuCl2(CO)L2] (L = PCy3 6d or PtBu2Me6e),
and the stereochemistry of the adducts, make a square pyram-
idal geometry the most plausible. In agreement with Caulton
and co-workers10 regarding π stabilization of unsaturation
in [RuH(X)(CO)(PtBu2Me)2], we propose a transoid arrange-
ment between the carbonyl and one of the chloride ligands,
delocalizing π donation by Cl. This hypothesis, in addition
to the non-equivalence of the phosphorus nuclei, places one
phosphine ligand trans to the vacant co-ordination site. In
support of this we note ∆δ (Table 1) in the 31P-{1H} NMR
spectrum of complex 1 in comparison to those of the adducts
[RuCl2(CO)(L)(PiPr2Me)2], which, maintaining the AB coup-
ling pattern in their 31P-{1H} NMR spectra, show a differ-
ent variation of δ for the phosphorus nuclei and a major
influence of the incoming ligand upon the phosphine trans to
the vacant site. Finally, the carbonyl group in compound 1
displays a triplet resonance in the 13C-{1H} NMR spectrum,
which is in accord with its disposition cis to both phosphine
ligands. This arrangement of the ligands is in contrast with
Results and discussion
Synthesis and structural characterization of the starting material
6d
those of the related [RuCl2(CO)L2] (L = PCy3 or PtBu2Me6e)
in which the apical position is occupied by the carbonyl
group.
In this paper we describe the synthesis and characterization of
J. Chem. Soc., Dalton Trans., 1999, 2399–2404
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Table 1 Chemical shifts, δ, of the 31P NMR signals, for complexes
showing a AB coupling pattern
Table 2 Selected bond distances (Å) and angles (Њ) for compound
[RuCl2(CO)(NH᎐CPh2)(PiPr2Me)2]. E.s.d.’s are in parenthesis.
᎐
Compound
L
δ P
δ PЈ
∆δ
1.2
25.3
24.4
5.1
2.0
3.2
8.5
Ru(1)–Cl(1)
Ru(1)–Cl(2)
Ru(1)–P(1)
Ru(1)–P(2)
Ru(1)–N(1)
2.481(2)
2.458(2)
2.373(2)
2.371(2)
2.144(5)
Ru(1)–C(1)
O(1)–C(1)
N(1)–C(2)
C(2)–C(3)
C(2)–C(9)
1.800(7)
1.167(7)
1.296(7)
1.469(9)
1.480(9)
1
2
3a
4
5
6
8a
—
CO
45.4
40.5
40.8
37.0
36.2
35.7
37.2
44.2
15.2
16.4
31.9
34.2
32.5
28.7
P
Cl
Cl
P
tBuNC
HNCPh2
Hpz
Ru
CO
Cl(1)–Ru(1)–Cl(2)
Cl(1)–Ru(1)–P(1)
Cl(1)–Ru(1)–P(2)
Cl(1)–Ru(1)–N(1)
Cl(1)–Ru(1)–C(1)
Cl(2)–Ru(1)–P(1)
Cl(2)–Ru(1)–P(2)
Cl(2)–Ru(1)–N(1)
Cl(2)–Ru(1)–C(1)
P(1)–Ru(1)–P(2)
85.44(6)
86.69(6)
94.82(6)
79.5(1)
177.5(2)
169.29(6)
82.23(6)
83.6(1)
P(1)–Ru(1)–N(1)
P(1)–Ru(1)–C(1)
P(2)–Ru(1)–N(1)
P(2)–Ru(1)–C(1)
N(1)–Ru(1)–C(1)
Ru(1)–N(1)–C(2)
Ru(1)–C(1)–O(1)
N(1)–C(2)–C(3)
N(1)–C(2)–C(9)
C(3)–C(2)–C(9)
87.8(1)
92.8(2)
165.1(1)
87.7(2)
L
3,5-Me2Hpz
2-PySH
98.0(2)
Reactions with CO and tBuNC
143.6(4)
176.8(6)
119.9(6)
121.3(5)
118.7(5)
The unsaturated character of complex 1 is evidenced by the
easy incorporation of neutral ligands in the co-ordination
sphere of the ruthenium. When carbon monoxide is bubbled
through a CH2Cl2 solution of 1 the colour rapidly changes from
yellow to colourless. The dicarbonyl complex [RuCl2(CO)2-
(PiPr2Me)2] 2 is isolated as a white microcrystalline solid. Two
intense absorptions appear at 1979 and 2053 cmϪ1 in the IR
spectrum and the phosphorus nuclei show a two doublet
pattern in the 31P-{1H} NMR spectrum. These data are consist-
ent with an all cis disposition around the ruthenium atom,
in contrast with that in the related complexes cis,cis,trans-
[RuCl2(CO)2(PiPr3)2],11 all-trans-[RuCl2(CO)2(L)2] (L = PtBu2-
94.7(2)
105.70(6)
9
Me6e or PEt3 ) and also with cis,trans-[RuH(Cl)(CO)2L2]
(L = PiPr3,6a PtBu2Me6b or PCy3 12), all of which show a trans
phosphine arrangement. We note that even phosphines with
less steric requirements like PPh3 or PEt3 prefer to form
complexes maintaining a relative trans configuration.8,9
Treatment of complex 1 with tert-butyl isocyanide in THF
gives the corresponding adduct 3a as a white solid in good
yield, and spectroscopically very similar to 2. However, if this
reaction is carried out in CH2Cl2 the resulting white solid 3b
exhibits only a singlet resonance in the 31P-{1H} NMR spec-
trum. The 13C-{1H} NMR resonance of the carbonyl group
appears as a low field triplet for both 3a and 3b, confirming the
presence of the two phosphines. This behaviour is not observed
in the formation of the dicarbonyl complex 2. The reason for
this must involve the better σ-donor character of the iso-
cyanide, allowing the rearrangement of the complex to a dis-
position in which the phosphine ligands become magnetically
equivalent. The distinction between cis- or trans-phosphines
only may be made from the coupling pattern of the methyl
groups PiPr2Me in the 13C-{1H} NMR spectrum, which instead
of the virtual triplet expected for a trans-diphosphine shows a
multiplet centred at δ 6.1 for 3b. This pattern is also observed
with other complexes described later.
Fig. 1 An ORTEP15 drawing of the compound [RuCl2(CO)(NHCPh2)-
(PiPr2Me)2] 4.
recrystallized from 1:1 CH2Cl2–Et2O gave suitable crystals for
X-ray diffraction (Fig. 1). This structure confirms some of our
hypothesis about the disposition of the ligands in the parent
complex 1. The co-ordination geometry around the ruthenium
atom can be described as a distorted octahedron with the two
phosphorus atoms of the diisopropylmethylphosphine ligands
in cis positions and the two chlorine atoms also occupying cis
positions. The carbonyl ligand is trans in relation to one of the
chloride ligands and if its direction is defined as axial the per-
pendicular plane is formed by two phosphorus, the other chlor-
ine and the nitrogen atom which is in trans relation to one
phosphorus. The π electronic influences can explain the fact
that the best π acceptor is opposite to the best π-donor ligand.
All distances and angles around ruthenium are in the normal
range (Table 2). The P(1)–Ru(1)–P(2) angle is 105.70(6)Њ
because of the steric demand of the bulky monodentate
phosphine substituents. The distance Ru(1)–N(1) 2.144(5) Å is
typical for a Ru–N single bond and is also similar to Os–N
distances previously found in osmium imine complexes.16
Angles around N(1) and C(2) show that both have sp2 char-
acter, Ru(1)–N(1)–C(2) 143.6(4)Њ being bigger than the ideal
120Њ because of the smaller size of the hydrogen atom.
Reactions with N-donor ligands
Complex 1 readily forms adduct complexes with N-donor lig-
ands like pyrazole, 3,5-dimethylpyrazole and even with diphe-
nylmethanimine despite the weak nucleophilic character of the
N atom in imine derivatives.13 Thereby, the treatment of 1 with
a slight excess of these reagents yielded the corresponding cis-
diphosphine adducts [RuCl2(CO)(L)(PiPr2Me)2] (L = NHCPh2
4, Hpz 5 or 3,5-Me2Hpz 6); each one shows in the IR spectra
the ν(N–H) absorption between 3200 and 3300 cmϪ1. The pyra-
zole derivatives 5 and 6 show a double ν(N–H) band due to the
possibility of the existence of N-H ؒ ؒ ؒ Cl interactions with the
neighbouring chlorides.11,14 Complexes 4–6 show in the 1H
NMR spectra at low field the corresponding signal for the NH
proton, as a broad singlet.
Crystal structure of complex [RuCl (CO)(NH᎐CPh )-
᎐
2
2
(PiPr2Me)2] 4
Reactions with benzenethiol and 2-sulfanylpyridine
Diphenylmethanimine reacts with complex 1 quickly and
cleanly, yielding a yellow microcrystalline solid which when
Research into the chemistry of sulfur compounds has identi-
fied many modes of co-ordination and the reactivity pattern of
2400
J. Chem. Soc., Dalton Trans., 1999, 2399–2404

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their complexes.17 Co-ordination complexes of neutral thiols
are relatively uncommon presumably because of the high acid-
ity of the SH functionality.18 Complex 1 reacts immediately
with benzenethiol affording a clear change from yellow to
green, but not leading to a simple co-ordination of the neutral
ligand. Evidence for the deprotonated nature of the ligand
comes from the non-observation of the band ν(SH) near 2500
cmϪ1 in the IR spectrum, nor the corresponding 1H NMR
signal for the proton of co-ordinated thiol. The 1H NMR
spectrum shows broad signals corresponding to the protons of
the phenyl ring of the thiophenolate ligand. Similar behaviour
has been found for the five-co-ordinate thiolate complex
[Ru(SPh)(dippe)2][BPh4]19 (dippe = iPr2PCH2CH2PiPr2) and
thiolate-bridged complexes.20 Thereby, the result of the direct
interaction of complex 1 with benzenethiol is the elimination of
HCl in polar solvents to give the product 7, but its mono- or bi-
nuclear nature cannot be distinguished only by NMR data. The
IR spectrum shows the ν(CO) absorption split into two peaks,
which seems to support the existence of a binuclear species with
thiolate or chloride bridges. The definitive proof comes from
mass spectrometry, which shows two peaks of the same inten-
sity corresponding to the fragments [M Ϫ PhS]ϩ and [M Ϫ
Cl]ϩ, where the molecular weight of M matches exactly with
a binuclear mixed-bridge complex [{RuCl(CO)(PiPr2Me)2}2-
(µ-Cl)(µ-SPh)] 7. The broadness of the signals in the 1H
NMR spectrum may be interpreted in terms of inversion at the
pyramidal bridging sulfur atom.20
In contrast with this, the reaction of complex 1 with 2-sulfanyl-
pyridine (PySH) affords the mononuclear product of addition
[RuCl2(CO)(PySH)(PiPr2Me)2] 8 as a mixture of the isomeric
complexes 8a and 8b. When the 8a/8b mixture is left in methyl-
ene chloride the concentration of 8a decreases till disappear-
ance, and 8b becomes the only product. Monitoring the
reaction by 31P-{1H} NMR at room temperature reveals the
initial formation of a two doublets resonance corresponding to
a cis disposition of the phosphines, which immediately
decreases giving rise to a singlet at δ 27.8, indicating that 8a and
8b are the kinetic and thermodynamic reaction products,
respectively. This singlet corresponds to the presence of two
equivalent phosphines. In the 13C-{1H} NMR spectrum of 8b,
the carbonyl ligand gives rise to a triplet signal at δ 200.3 with
2JCP = 14 Hz. The distinction between magnetically equivalent
cis- or trans-phosphines is related to that in complex 3b,
because both compounds exhibit identical patterns for the
PiPr2Me carbon atom. The IR spectra of 8a and 8b show a
weak band near 3200 cmϪ1 instead of ν(SH). This band is
consistent with the presence of broad resonances at δ 14.4 and
14.8 respectively, in their 1H NMR spectra, attributable to
nitrogen-bound protons, which suggests that PySH exists as its
1H-pyridine-2-thione tautomeric form in this complex. This
tautomeric process in 2-sulfanylpyridine is well established21
and shows that the thione co-ordinates exclusively via the S
atom, in contrast with the thiolate, which can adopt a variety of
co-ordination modes. Recently, we have found the same co-
ordination mode of PySH in [RuCp(PiPr2Me)(PPh3)(PySH)]-
[BPh4] and other related complexes.22
CO
Ru
Cl
P
P
P
S
S
OC
Cl
S
S
Ru
P
Fig. 2 Possible configurations for complex 9 maintaining phosphine
ligands magnetically equivalent.
Fig. 3 The protons Ha and HaЈ become magnetically non-equivalent
because the indicated plane is not a plane of symmetry of the molecule.
of the chloride is selective, affording only one of the two
possible isomeric products.
In all cases, one singlet is observed in the 31P-{1H} NMR
spectra, corresponding to two equivalent phosphines because
of the triplet resonance of the carbonyl group in the 13C-{1H}
NMR spectra, which indicates a cis arrangement with the two
phosphine ligands. The unequivocal distinction between cis- or
trans-phosphine disposition could be accomplished from the
full interpretation of the 1H, COSY, 13C-{1H} and 31P-{1H}
NMR spectra of the diethyldithiocarbamate complex 9 (Fig. 2).
1
The ethyl groups exhibit in the H NMR spectrum a triplet
signal for the methyl, whereas the methylene signal is split into
two multiplets. Since the two ethyl groups proved to be equiv-
alent in the 13C-{1H} NMR spectrum, showing only two singlet
1
resonances, the duplicity of the methylene signals in the H
NMR spectrum only can be explained by the non-equivalence
of the diastereotopic methylene protons.17a The C–N bond in
the η2-dithiocarbamate ligand is not single, ν(C᎐N) 1505 cmϪ1
᎐
in the IR spectrum, maintaining the adjacent atoms in the same
plane (Fig. 3). This plane is not a plane of symmetry of the
molecule, resulting in the non-equivalence of the methylene
protons. We propose for this compound a structure with the
group S2P2 disposed in the equatorial plane, which is the unique
arrangement consistent with these spectral data.
Dithiocarbonate complexes 10–12 gave spectral data and
patterns almost identical to those of the dithiocarbamate com-
pound, with slight variations in δ attributable to their different
donor character, and with the reasonable differences due to the
diverse O-bonded alkyl groups. The most obvious divergence
corresponds to the more electropositive ROCS2 carbon atom of
the dithiocarbonates which appears as a singlet near δ 230,
while the analogous Et2NCS2 in dithiocarbamate appears at δ
211, in the 13C-{1H} NMR spectra. In this case, no irregularities
1
in the H NMR spectrum of the dithiocarbonate derivatives
have been observed for the resonances corresponding to the
alkyl groups.
Metathesis reactions with bidentate ligands
Metathesis reactions of complex 1 with salts of diethyldithio-
carbamate and o-alkyl dithiocarbonates afforded the neutral
chelate complexes [RuCl(η2-S2CNEt2)(CO)(PiPr2Me)2] 9 and
[RuCl(η2-S2COR)(CO)(PiPr2Me)2] (R = Me 10, Et 11 or iPr 12).
Our recent study on these bidentate ligands showed the pos-
sibility of η1 or η2 co-ordination depending on the particular
complex,22 but in this instance the presence of a vacant co-
ordination site and two metathetically exchangeable chloride
ligands next to it makes η2 co-ordination the most favourable
process. This reaction takes place with a very high yield even
under moderate conditions in a few hours, and the replacement
All the complexes showing singlet resonances in their 31P-
{1H} NMR spectra (3b, 8b and 9–12) display identical coupling
patterns in the 13C-{1H} NMR spectra for the carbons directly
bonded to the phosphorus atom. The spectral data of 3b and 8b
do not allow one to decide if the mutual disposition of the
phosphines is cis or trans, but on the basis of this similitude we
propose a magnetically equivalent cis configuration.
The ruthenium complex 1 reacts with potassium acetylaceto-
nate in CH2Cl2 to afford the corresponding β-diketonato com-
plex [RuCl(acac)(CO)(PiPr2Me)2] 13. The IR spectrum shows
the presence of two ν(CO) bands at 1520 and 1590 cmϪ1 assign-
J. Chem. Soc., Dalton Trans., 1999, 2399–2404
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using the TEXSAN26 software system and ORTEP15 for
plotting.
Table 3 Summary of crystal data and crystal structure analysis for
compound [RuCl2(CO)(NH᎐CPh2)(PiPr2Me)2]
᎐
CCDC reference number 186/1484.
See http://www.rsc.org/suppdata/dt/1999/2399/ for crystallo-
graphic files in .cif format.
Chemical formula
M
Crystal system
Space group
a/Å
b/Å
c/Å
C28H45Cl2NOP2Ru
645.59
Monoclinic
P21
9.204(4)
17.129(4)
10.041(4)
104.65(3)
1531.4(9)
290.2
Preparations
[RuCl2(CO)(PiPr2Me)2] 1. To a solution of RuCl3ؒxH2O
(0.50 g, 2.5 mmol) in 2-methoxyethanol (10 ml) was added the
phosphine PiPr2Me (1.2 ml, 8 mmol). The resulting mixture was
heated under reflux with continuous stirring for 24 h. After
removing the solvent under reduced pressure, ethanol (10 ml)
and light petroleum (10 ml) were added to the residue, yielding
the precipitation of a yellow solid, which was filtered off,
washed with light petroleum and acetone, and dried under
vacuum. Yield: 1 g (86%). Calc. C15H34Cl2OP2Ru: C, 38.8; H,
7.32. Found: C, 39.1; H, 7.27%. IR (Nujol, cmϪ1): ν(CO) 1939.
1H NMR (400 MHz, 293 K, CDCl3): δ 1.18–1.37 (m, 24 H,
PCH(CH3)2), 1.42 and 1.44 (d, 3 H each, 2JHP = 7.2, 2JHPЈ = 7.6
Hz, PCH3), 2.39 and 2.52 (m, 2 H each, PCH(CH3)2). 31P-{1H}
NMR (161.89 MHz, CDCl3, 273 K): δ 44.2 and 45.4 (d,
2JPPЈ = 23.2 Hz). 13C-{1H} NMR (50.31 MHz, 293 K, CDCl3):
β/Њ
V/Å3
T/K
Z
2
8.01
µ(Mo-Kα)/cmϪ1
Unique reflections
Observed reflections (I > 3σ)
R
RЈ
2915 (Rint = 0.143)
2452
0.0289
0.0353
able to bidentate O-bonded acac.23 The 1H NMR spectrum
exhibits two methyl resonances of equal intensity at δ 1.90 and
1.95, and the 13C-{1H} NMR spectrum displays two signals for
the methyl carbons and two for the ketonic carbons, indicative
of chelate acac bound trans to an asymmetric ligand pair, in
accord with the data observed for the analogous complex
[RuCl(acac)(CO)(PPh3)2].24 The 31P-{1H} NMR spectrum con-
sists of two doublet resonances, in contrast with the chelate
complexes 9–12. These data allow one to conclude that this
metathesis reaction leads to selective substitution of the other
chloride group of the complex, showing a different preference
between S- and O-donor ligands.
1
1
δ 8.13 and 8.70 (d, JCP = 22.2, JCPЈ = 22.7, PCH3), 18.0, 18.9
and 19.3 (m, PCH(CH3)2), 27.0, 27.6, 28.0 and 28.5 (d,
1JCP = 15.9, 17.2, 10.6, 10.2, PCH(CH3)2) and 199.5 (t,
2JCP = 2JCPЈ = 16.7 Hz, CO).
[RuCl2(CO)2(PiPr2Me)2] 2. Carbon monoxide was bubbled
through a solution of complex 1 (0.11 g, 0.25 mmol) in CH2Cl2
(10 ml) for 5 min at room temperature, causing an immediate
change to colourless. The mixture was stirred for 30 min
under a CO atmosphere, and then the removal of the solvent in
vacuum yielded a white solid, which was washed with light
petroleum and dried. Yield: 0.12 g (100%). Calc. for C16H34Cl2-
P2O2 Ru: C, 39.0; H, 6.91. Found: C, 39.8; H, 6.87%. IR (Nujol,
cmϪ1): ν(CO) 2053, 1971. 1H NMR (400 MHz, 293 K, CDCl3):
δ 1.20–1.32 (m, 24 H, PCH(CH3)2), 1.52 and 1.54 (d, 3 H each,
Experimental
General procedures
All synthetic operations were performed under a dry dinitrogen
or argon atmosphere following conventional Schlenk tech-
niques. The solvents THF, Et2O, and light petroleum (boiling
point range 40–60 ЊC) were distilled from the appropriate
drying agents. All solvents were deoxygenated immediately
before use. The compound PiPr2Me was obtained by reaction
of PiPr2Cl (Aldrich) with MgMeI in Et2O. The IR spectra were
recorded in Nujol mulls on a Perkin-Elmer FTIR Spectrum
1000 spectrophotometer, NMR spectra on Varian Unity 400
MHz or Varian Gemini 200 MHz spectrometers. Chemical
shifts are given in ppm from SiMe4 (1H and 13C-{1H}) or 85%
H3PO4 (31P-{1H}). Microanalyses were performed by the
Serveis Científico-Tècnics, Universitat of Barcelona. Electro-
spray ionization mass spectrometry (ESI-MS) was performed
on a VG Platform single-quadrupole mass spectrometer
(Micromass Instruments, Altrincham, UK) equipped with an
electrospray ionization source, operating in the positive-ion
mode at a probe tip voltage of ϩ3.5 kV. The extraction cone
voltage was varied from ϩ35 to Ϫ35 V.
2
2JHP = 4.5, JHPЈ = 4.1 Hz, PCH3), 2.20, 2.47, 2.65 and 2.67 (m,
1 H each, PCH(CH3)2). 31P-{1H} NMR (161.89 MHz, CDCl3,
2
273 K): δ 15.2 and 40.5 (d, JPPЈ = 23.3 Hz). 13C-{1H} NMR
1
(50.31 MHz, 293 K, CDCl3): δ 3.47 and 8.94 (d, JPC = 26.3,
1JPЈC = 30.2, PCH3), 17.8–18.7 (m, PCH(CH3)2), 24.5, 25.2, 28.2,
1
28.9 (d, JCP = 22.4, 23.1, 28.0 and 26.5, PCH(CH3)2), 188.9 (s,
CO) and 195.5 (dd, 2JCP = 2JCPЈ = 12.3 Hz, CO).
[RuCl2(CO)(tBuNC)(PiPr2Me)2] 3a and 3b. Complex 3a. To a
suspension of complex 1 (0.11 g, 0.25 mmol) in THF (10 ml)
was added tert-butyl isocyanide (55 µl, 0.50 mmol) yielding a
colourless solution after 5 min. The solution was stirred for 30
min more, concentrated to ca. 2 ml and by addition of light
petroleum a white solid precipitated. Yield: 0.13 g (93%). Calc.
for C20H43Cl2NOP2Ru: C, 43.8; H, 7.85. Found: C, 42.8; H,
7.82%. IR (Nujol, cmϪ1): ν(CO) 1948, ν(CN) 2180. H NMR
1
(400 MHz, 293 K, CDCl3): δ 1.22–1.35 (m, 24 H, PCH(CH3)2),
2
2
1.50 and 1.52 (d, 3 H each, JHP = 8.7, JHPЈ = 9.1 Hz, PCH3),
1.54 (s, 9 H, CNC(CH3)3), 2.25, 2.50, 2.56 and 2.63 (m, 1 H
each, PCH(CH3)2). 31P-{1H} NMR (161.89 MHz, CDCl3, 273
Structure determination of [RuCl (CO)(NH᎐CPh )(PiPr Me) ]
᎐
2
2
2
2
4
2
Details are given in Table 3. Data collection was carried out
using an AFC6S-Rigaku automatic diffractometer in the ω–2θ
scan mode with monochromated Mo-Kα radiation. The struc-
ture was solved by Patterson methods and subsequent expan-
sion of the models using DIRDIF.25 Reflections having I > 3σ(I)
were used for structure refinement. All non-hydrogen atoms
were anisotropically refined. The hydrogen atoms were included
at idealized positions and not refined. Since the space group is
non-centrosymmetric both enantiomorphs were checked and
no significant differences found between them. All calcu-
lations for data reduction, structure solution, and refinement
were carried out on a VAX 3520 computer at the Servicio
Central de Ciencia y Tecnología de la Universidad de Cádiz,
K): δ 16.4 and 40.8 (d, JPPЈ = 24.0 Hz). 13C-{1H} NMR (50.31
1
MHz, 293 K, CDCl3): δ 3.0 (t, JPC = 1JPЈC = 25.2, PCH3), 18.0,
18.2, 18.9 and 19.0 (s, PCH(CH3)2), 26.1 and 26.7 (t, 1JCP = 22.0,
25.5, PCH(CH3)2), 30.6 (s, CNC(CH3)3), 54.4 (s, CNC(CH3)3),
157.6 (s, CNC(CH3)3) and 201.0 (t, 2JCP = 15 Hz, CO).
Complex 3b. To a solution of complex 1 (0.11 g, 0.25 mmol)
in CH2Cl2 (10 ml) was added tert-butyl isocyanide (55 µl, 0.50
mmol), resulting in a change to colourless. After stirring for 30
min at room temperature, the solvent was removed under vac-
uum, yielding a white solid which was washed with diethyl ether
and dried. Yield: 0.15 g (96%). Calc. for C20H43Cl2NOP2Ru: C,
43.8; H, 7.85. Found: C, 43.9; H, 7.88%. IR (Nujol, cmϪ1):
ν(CO) 1969, ν(CN) 2180 and 2206. 1H NMR (400 MHz, 293 K,
2402
J. Chem. Soc., Dalton Trans., 1999, 2399–2404

View Article Online
CDCl3): δ 1.20–1.32 (m, 12 H, PCH(CH3)2), 1.47 (d, 3 H,
2JHP = 9.0 Hz, PCH3), 1.60 (s, 9 H, CNC(CH3)3), 2.26 and 2.47
(m, 1H each, PCH(CH3)2). 31P-{1H} NMR (161.89 MHz,
CDCl3, 273 K): δ 20.1 (s). 13C-{1H} NMR (50.31 MHz, 293 K,
CDCl3): δ 6.07 (m, PCH3), 18.0, 18.2, 18.6 and 19.0 (s,
PCH(CH3)2), 25.8 and 27.4 (m, PCH(CH3)2), 30.2 (s,
CNC(CH3)3), 59.6 (s, CNC(CH3)3), 163.5 (s, CNC(CH3)3) and
195.0 (t, 2JCP = 13.2 Hz, CO).
7.34%. IR (Nujol, cmϪ1): ν(CO) 1967 and 1949. 1H NMR (400
MHz, 293 K, CD3COCD3): δ 1.0–1.4 (m, 24 H, PCH(CH3)2),
2
2
1.58 and 1.61 (d, 3 H each, JHP = 4.8, JHPЈ = 5.5 Hz, PCH3),
2.47, 2.55 and 2.72 (m, 4 H, PCH(CH3)2), 7.31 and 8.24 (m, 5 H,
C6H5S). 31P-{1H} NMR (161.89 MHz, 273 K, CD3COCD3):
δ 44.7 and 29.2 (d, 2JPPЈ = 20.5 Hz). 13C-{1H} NMR (50.31 MHz,
293 K, CD3COCD3): δ 7.98 and 9.18 (d, 1JCP = 27.5, 1JCPЈ = 32.0
Hz, PCH3), 18.23–19.8 (m, PCH(CH3)2), 27.3, 28.2, 28.5 and
1
29.8 (d, JCP = 27.3, 28.2, 28.5 and 29.8, PCH(CH3)2), 128.4,
[RuCl2(CO)(NHCPh2)(PiPr2Me)2] 4. A solution of complex
1 (0.11 g, 0.25 mmol) in CH2Cl2 was treated with diphenyl-
methanimine (53 µl, 0.30 mmol) and stirred for 2 h. Solvent
evaporation under vacuum left a yellow solid, which was
washed with light petroleum. The crude product was recrystal-
lized from a two-layered solution of CH2Cl2 and light petrol-
eum (1:1). Yield: 0.15 g (94%). Calc. for C28H45Cl2NOP2Ru: C,
52.0; H, 6.97. Found: C, 52.5; H, 7.09%. IR (Nujol, cmϪ1):
ν(CO) 1936, ν(NH) 3217. 1H NMR (400 MHz, 293 K, CDCl3):
δ 1.12–1.43 (m, 24 H, PCH(CH3)2), 0.96 and 1.05 (dd, 3 H each,
128.9, 129.1 and 134.9 (s, C6H5S), 203.1 (t, JCP = 2JCPЈ = 16.6
2
Hz, CO). Mass spectrum (ESI-MS): m/z 967 (M Ϫ SPh, 100%)
and 895 (M Ϫ Cl, 100%).
[RuCl2(CO)(PySH)(PiPr2Me)2] 8a and 8b. A solution of
complex 1 (0.11 g, 0.25 mmol) in CH2Cl2 (10 ml) was treated
with an excess of 2-sulfanylpyridine (56 mg, 0.50 mmol) with
continuous stirring at room temperature for 30 min, and a
gradual change from yellow to red was observed. The solvent
was removed in vacuum and the residue washed with Et2O,
isolating a red solid which mostly corresponds to complex 8a. If
the reaction is stirred for more than 4 h, 8b is the only product.
Yield: 0.13 g (90%). Calc. for C20H39Cl2NOP2RuS: C, 41.7; H,
2
2JHP = 7.0, JHPЈ = 6.9 Hz, PCH3), 2.04, 2.18, 2.90 and 2.95 (m,
1 H each, PCH(CH3)2), 7.38, 7.48 and 7.83 (m, 10 H,
HNC(C6H5)2) and 10.8 (br s, HNCPh2). 31P-{1H} NMR (161.89
2
MHz, CDCl3, 273 K): δ 31.9 and 37.0 (d, JPPЈ = 26.8 Hz).
6.78. Found: C, 41.2; H, 6.84%. Complex 8a: IR (Nujol, cmϪ1
)
13C-{1H} NMR (50.31 MHz, 293 K, CDCl3): δ 6.14 and 6.67 (d,
1JPC = 1JPЈC = 12.9, PCH3), 18.1, 19.2 and 20.0 (m, PCH(CH3)2),
ν(NH) 3182, ν(CO) 1931, ν(C᎐C/C᎐N) 1606, 1587; H NMR
1
᎐
᎐
(400 MHz, 293 K, CDCl3) δ 1.18–1.32 (m, 24 H, PCH(CH3)2),
1
2
25.3, 26.6, 27.1 and 28.5 (d, JCP = 28.3, 24.5, 24.7 and 25.6,
1.42 and 1.44 (d, 3 H each, JHP = 2JHPЈ = 8.2, PCH3), 2.65 and
3
PCH(CH3)2), 128.1, 128.7, 129.1, 130.1, 130.3, 131.5, 137.0 and
138.4 (s, HNC(C6H5)2), 179.5 (s, HNC(C6H5)2) and 200.5 (t,
2JCP = 15.5 Hz, CO).
2.80 (m,
᎐
᎐
2
H
each, PCH(CH3)2), 6.78 (t, JHH = 6.4,
S᎐CCHCH), 7.42 (t, 3JHH = 6.0, NCHCH), 7.54 (d, 3JHH = 6.0,
3
S᎐CCH), 7.89 (t, JHH = 6.0 Hz, NCH) and 14.39 (br s, NH);
31P-{1H} NMR (161.89 MHz, CDCl3, 273 K) δ 28.7 and 37.2
[RuCl2(CO)(L)(PiPr2Me)2] (L ؍ Hpz 5 or 3,5-Me2Hpz 6).
These compounds were prepared in a similar way to the previ-
ous imine adduct, with the reagents pyrazole (34 mg, 0.50
mmol) or 3,5-dimethylpyrazole (48 mg, 0.50 mmol) respect-
ively, stirring the mixtures for 4 h and yielding a greenish white
and a brown solid respectively.
(d, JPPЈ = 24 Hz); 13C-{1H} NMR could not be obtained
2
because of the quickness of the isomerization process. Complex
8b: IR (Nujol, cmϪ1) ν(NH) 3182, ν(CO) 1939, ν(C᎐C/C᎐N)
᎐
᎐
1
1608, 1580; H NMR (400 MHz, 293 K, CDCl3) δ 1.18–1.32
(m, 24 H, PCH(CH3)2), 1.42 (d, 6 H, JHP = 8.3, PCH3), 2.68
3
and 2.80 (m, 2 H each, PCH(CH3)2), 6.92 (t, JHH = 6.4,
Complex 5. Yield 0.09 g (68%). Calc. for C18H38Cl2N2OP2Ru:
C, 40.6; H, 7.14. Found: C, 40.1; H, 7.29%. IR (Nujol, cmϪ1):
ν(CO) 1928, ν(NH) 3123 and 3331. 1H NMR (400 MHz, 293 K,
CDCl3): δ 0.90–1.42 (m, 30 H, PCH(CH3)2 and PCH3), 2.13 and
2.86 (m, 2 H each, PCH(CH3)2), 6.38, 7.58 and 7.76 (s, 1 H
each, C3H3N2) and 12.58 (br s, 1 H, NH). 31P-{1H} NMR
S᎐CCHCH), 7.39 (t, 3JHH = 6.4, NCHCH), 7.63 (d, 3JHH = 8.0,
᎐
᎐
3
S᎐CCH), 8.13 (t, JHH = 6.0 Hz, NCH) and 14.78 (br s,
NH); 31P-{1H} NMR (161.89 MHz, CDCl3, 273 K) δ 27.8 (s);
13C-{1H} NMR (50.31 MHz, 293 K, CDCl3) δ 5.8 (m, PCH3),
17.6, 18.1 and 18.9 (s, PCH(CH3)2), 25.9 and 26.3 (m,
PCH(CH3)2), 116.3 (s, SCCHCH), 130.8, 137.4, and 138.5 (s,
NCHCH and S᎐CCH), 169.6 (s, S᎐CN) and 200.3 (t, 1JCP=14.1
2
(161.89 MHz, CDCl3, 273 K): δ 34.2 and 36.2 (d, JPPЈ = 26.7
᎐
᎐
Hz). 13C-{1H} NMR (50.31 MHz, 293 K, CDCl3): δ 6.12 and
Hz, CO).
1
6.92 (d, JPC = 1JPЈC = 26.7, PCH3), 17.8–19.8 (m, PCH(CH3)2),
1
25.6, 26.7, 27.0 and 28.8 (d, JCP = 27.8, 25.1, 25.4 and 25.4,
[RuCl(S2CNEt2)(CO)(PiPr2Me)2] 9. To a solution of complex
1 (0.11 g, 0.25 mmol) in CH2Cl2 (10 ml) was added sodium
diethyldithiocarbamate (51 mg, 0.30 mmol). The resulting sus-
pension was stirred for 12 h and then filtered through Celite.
Removal of the solvent by vacuum afforded a brown micro-
crystalline solid which was washed with light petroleum. Yield:
0.14 g (97%). Calc. for C20H44ClNOP2RuS2: C, 41.6; H, 7.62.
Found: C, 40.9; H, 7.47%. IR (Nujol, cmϪ1): ν(CO) 1921,
ν(C᎐N) 1505. 1H NMR (400 MHz, 293 K, CDCl ): δ 1.17–1.35
PCH(CH3)2), 107.2, 129.3 and 141.7 (s, C3H3N2) and 200.8 (dd,
2JCP=14.8, 2JCPЈ = 17.1 Hz, CO).
Complex 6. Yield 0.13 g (93%). Calc. for C20H42Cl2N2OP2Ru:
C, 42.8; H, 7.49. Found: C, 42.5; H, 7.30%. IR (Nujol, cmϪ1):
ν(CO) 1923, ν(NH) 3209 and 3250. 1H NMR (400 MHz, 293 K,
CDCl3): δ 0.98–1.39 (m, 24 H, PCH(CH3)2), 1.39 and 1.44 (d,
3 H each, 2JHP = 9.1, 2JHPЈ = 9.5 Hz, PCH3), 2.02, 2.36, 2.78 and
2.98 (m, 1 H each, PCH(CH3)2), 2.23 and 2.53 (s, 3 H each,
(CH3)2C3HN2), 5.85 (s, 1 H, (CH3)2C3HN2) and 12.26 (br s, 1 H,
NH). 31P-{1H} NMR (161.89 MHz, CDCl3, 273 K): δ 32.5 and
᎐
3
(m, 24 H, PCH(CH3)2), 1.40 (d, 6 H, 2JHP = 8.2 Hz, PCH3), 2.14
3
and 2.30 (m, 2 H each, PCH(CH3)2), 1.24 (t, 6 H, JHa,CH
=
3
2
35.7 (d, JPPЈ = 26.4 Hz). 13C-{1H} NMR (50.31 MHz, 293 K,
3JHb,CH = 7, S2CN(CHaHbCH3)2), 3.65 and 3.81 (m, 2 H
1
1
3 3
CDCl3): δ 6.20 and 7.34 (d, JCP = 27.0, JCPЈ = 26.5, PCH3),
18.21–19.97 (m, PCH(CH3)2), 26.0, 26.3, 26.8 and 28.1 (d,
1JCP = 25.3, 23.8, 28.0 and 25.7, PCH(CH3)2), 11.0 and 15.6 (s,
(CH3)2C3HN2), 107.6, 139.9 and 152.2 (s, (CH3)2C3HN2) and
200.2 (t, 2JCP = 15.6 Hz, CO).
each, JCH ,Ha = 3JCH ,Hb = 7 Hz, S2CN(CHaHbCH3)2). 31P-
{1H} NMR3 (161.89 MHz, CDCl3, 273 K): δ 30.9 (s). 13C-{1H}
NMR (50.31 MHz, 293 K, CDCl3): δ 6.80 (m, PCH3), 18.3, 18.8
and 19.3 (s, PCH(CH3)2), 27.4 and 28.2 (m, PCH(CH3)2), 12.3
3
2
(s, S2CN(CH2CH3)2), 43.1 (s, S2CN(CH2CH3)2, 200.9 (t, JCP
= 2JCPЈ = 13.8 Hz, CO) and 211.4 (s, S2CN(CH2CH3)2.
[{RuCl(CO)(PiPr2Me)2}2(ì-Cl)(ì-SPh)] 7. A solution of
complex 1 (0.11 g, 0.25 mmol) in CH2Cl2 (10 ml) was treated
with benzenethiol (51 µl, 0.50 mmol) with an immediate change
from yellow to green. The solution was stirred for 4 h. The
solvent was removed in vacuo and the residue washed with
Et2O, isolating a green solid. Yield: 0.11 g (88%). Calc. for
C36H73Cl3O2P4Ru2S: C, 43.1; H, 7.34%. Found: C, 43.3; H,
i
[RuCl(S2COR)(CO)(PiPr2Me)2] (R ؍ Me 10, Et 11 or Pr
12). An experimental procedure identical to that for 9 was
followed for the preparation of these complexes, using the
corresponding potassium alkyl dithiocarbonate KS2COR
(0.3 mmol). The compounds were recrystallized from CH2Cl2
by slow evaporation of the solvent.
J. Chem. Soc., Dalton Trans., 1999, 2399–2404
2403

View Article Online
J. Organomet. Chem., 1989, 336, 187; M. A. Esteruelas, J. Herrero
and L. A. Oro, Organometallics, 1993, 12, 2377.
2 C. Slugovc, D. Doberer, C. Gemel, R. Schmid, K. Kirchner,
B. Winkler and F. Stelzer, Monatsh. Chem., 1998, 129, 221;
S. Maddock, R. Clifton, W. Roper and L. J. Wright, Organo-
metallics, 1996, 15, 1973.
3 G. R. Clark, G. J. Irvine, W. R. Roper and L. J. Wright, Organo-
metallics, 1997, 16, 5499.
4 H. Werner, C. Grünwald, P. Steinert, O. Gevert and J. Wolf,
J. Organomet. Chem., 1998, 565, 231.
5 (a) C. Li, M. Ogasawara, S. P. Nolan and K. G. Caulton,
Organometallics, 1996, 15, 4900; (b) S. T. Nguyen, R. H. Grubbs
and J. W. Ziller, J. Am. Chem. Soc., 1993, 115, 9858; P. Schwab, R. H.
Grubbs and J. W. Ziller, J. Am. Chem. Soc., 1996, 118, 100.
6 (a) M. A. Esteruelas and H. Werner, J. Organomet. Chem., 1986,
303, 221; (b) D. F. Gill and B. L. Shaw, Inorg. Chim. Acta, 1979, 32,
19; (c) F. G. Moers and J. P. Langhout, Recl. Trav. Chim. Pays Bas,
1972, 91, 591; (d) F. G. Moers, P. T. Buerskens and J. H. Noordik,
Cryst. Struct. Commun., 1982, 11, 1655; (e) D. Huang, K. Folting
and K. G. Caulton, Inorg. Chem., 1996, 35, 7035.
7 J. Espuelas, M. A. Esteruelas, F. J. Lahoz, L. A. Oro and C. Valero,
Organometallics, 1993, 12, 663 and refs. therein; M. L. Buil, S. Elipe,
M. A. Esteruelas, E. Oñate, E. Peinado and N. Ruiz, Organo-
metallics, 1997, 16, 5748 and refs. therein.
8 H. P. Xia, R. C. Yeung and G. Jia, Organometallics, 1998,
17, 4762; R. B. Bedford, A. F. Hill, C. Jones, A. J. White, D. J.
Williams and J. D. Wilton-Ely, Organometallics, 1998, 17, 4744;
Y. Maruyama, K. Yamamura, I. Nakayama, K. Yoshiuchi and
F. Ozawa, J. Am. Chem. Soc., 1998, 120, 1421; B. Marciniec,
C. Pietraszuk and M. Kujawa, J. Mol. Catal. A. Chem., 1998, 133,
41.
Complex 10. Yield: 0.13 g (97%). Calc. for C17H37ClO2P2-
RuS2: C, 38.0; H, 6.90. Found: C, 37.8; H, 6.98%. IR (Nujol,
cmϪ1): ν(CO) 1928. 1H NMR (400 MHz, 293 K, CDCl3):
δ 1.19–1.33 (m, 24 H, PCH(CH3)2), 1.43 (d, 6 H, JHP = 8.5 Hz,
PCH3), 2.20 and 2.40 (m, 2 H each, PCH(CH3)2) and 4.14 (s,
3 H, S2COCH3). 31P-{1H} NMR (161.89 MHz, CDCl3, 273 K):
δ 32.8 (s). 13C-{1H} NMR (50.31 MHz, 293 K, CDCl3): δ 7.12
(m, PCH3), 18.3, 18.8 and 19.3 (s, PCH(CH3)2), 27.8 and 28.3
(m, PCH(CH3)2), 57.0 (s, S2COCH3), 199.2 (t, 2JCP = 2JCPЈ = 15.3
Hz, CO) and 230.9 (s, S2COCH3).
Complex 11. Yield: 0.13 g (94%). Calc. for C18H39ClO2P2-
RuS2: C, 39.3; H, 7.09. Found: C, 39.3; H, 7.19%. IR (Nujol,
cmϪ1): ν(CO) 1925. 1H NMR (400 MHz, 293 K, CDCl3):
δ 1.17–1.34 (m, 24 H, PCH(CH3)2), 1.42 (d, 6 H, JHP = 8.4,
PCH3), 2.16 and 2.38 (m, 2 H each, PCH(CH3)2), 1.41 (t, 3 H,
JCH ,CH = 7.2, S2COCH2CH3) and 4.59 (c, 2 H, JCH ,CH
=
2
2
3
7.2 3Hz, S2COCH2CH3). 31P-{1H} NMR (161.89 MHz, CDCl3,
273 K): δ 32.7 (s). 13C-{1H} NMR (50.31 MHz, 293 K, CDCl3):
δ 7.12 (m, PCH3), 18.3, 18.8 and 19.3 (s, PCH(CH3)2), 27.8 and
28.2 (m, PCH(CH3)2), 13.8 (s, S2COCH2CH3), 66.9 (s, S2CO-
2
CH2CH3), 199.3 (t, JCP = 2JCPЈ = 15 Hz, CO) and 230.2 (s,
S2COCH2CH3).
Complex 12. Yield: 0.14 g (100%). Calc. for C19H41ClO2P2-
RuS2: C, 40.4; H, 7.27. Found: C, 41.1; H, 7.26%. IR (Nujol,
cmϪ1): ν(CO) 1936. 1H NMR (400 MHz, 293 K, CDCl3):
2
δ 1.17–1.34 (m, 24 H, PCH(CH3)2), 1.42 (d, 6 H, JHP = 8.4,
3
PCH3), 1.40 (d, 6 H, JCH ,CH = 6.4, S2COCH(CH3)2), 2.16 and
3
9 Y. Sun, N. J. Taylor and A. J. Carty, J. Organomet. Chem., 1992,
C43, 423; Organometallics, 1992, 11, 4293.
10 J. T. Poulton, M. P. Sigalas, O. Eisenstein and K. G. Caulton, Inorg.
Chem., 1993, 32, 5490; J. T. Poulton, M. P. Sigalas, K. Folting,
W. Streib, O. Eisenstein and K. G. Caulton, Inorg. Chem., 1994, 33,
1476.
11 R. Atencio, C. Bohanna, M. A. Esteruelas, F. J. Lahoz and
L. A. Oro, J. Chem. Soc., Dalton Trans., 1995, 2171.
12 M. L. Christ, S. Sabo-Etienne and B. Chaudret, Organometallics,
1994, 13, 3800.
3
2.38 (m, 2 H each, PCH(CH3)2) and 5.57 (sept, JCH,CH = 6.4
3
Hz, S2COCH(CH3)2). 31P-{1H} NMR (161.89 MHz, CDCl3,
273 K): δ 32.5 (s). 13C-{1H} NMR (50.31 MHz, 293 K, CDCl3):
δ 7.1 (m, PCH3), 18.3, 18.8 and 19.3 (s, PCH(CH3)2), 27.9
and 28.2 (m, PCH(CH3)2), 21.8 (s, S2COCH(CH3)2), 75.6 (s,
2
S2COCH(CH3)2), 199.5 (t, JCP = 14 Hz, CO) and 229.7 (s,
S2COCH(CH3)2).
[RuCl(acac)(CO)(PiPr2Me)2] 13. To a solution of complex 1
(0.11 g, 0.25 mmol) in CH2Cl2 (5 ml) was added a suspension
formed by addition of potassium tert-butoxide (50 mg, 0.25
mmol) to 5 ml CH2Cl2–acetylacetone (1:1). The resulting
suspension was stirred for 12 h at room temperature and then
filtered through Celite. Removal of the solvent by vacuum
yielded a brown oil which was washed with Et2O. The oil sol-
idified at temperatures below Ϫ20 ЊC. Yield: 0.08 g (65%). Calc.
for C20H41ClO3P2Ru: C, 45.5; H, 7.77. Found: C, 45.1; H,
7.80%. IR (Nujol, cmϪ1): ν(CO) 1940, ν(COacac) 1590 and 1520.
1H NMR (400 MHz, 293 K, CDCl3): δ 1.04–1.31 (m, 30 H,
PCH(CH3)2 and PCH3), 2.15, 2.20, 2.61 and 2.68 (m, 2 H each,
PCH(CH3)2), 1.90 and 1.95 (s, 3 H each, CH3COCHCOCH3)
and 5.36 (s, 1 H, CH3COCHCOCH3). 31P-{1H} NMR (161.89
13 R. C. Mehrora, in Comprehensive Coordination Chemistry, eds.
G. Wilkinson, R. D. Gillard and J. A. McCleverty, Pergamon,
Oxford, 1987, vol. 2, p. 269; H. Elsbernd and J. K. Beattie, J. Chem.
Soc. A, 1970, 2598; B. C. Lane, J. E. Lester and F. Basolo, Chem.
Commun., 1971, 1618; S. Joss, P. Bigler and A. Ludi, Inorg. Chem.,
1985, 24, 3487; W. D. Harman and H. Taube, Inorg. Chem., 1988, 27,
3261.
14 D. Carmona, J. Ferrer, L. A. Oro, M. C. Apreda, M. C. C. Foces-
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2
MHz, CDCl3, 273 K): δ 38.5 and 42.9 (d, JPPЈ = 26.3 Hz).
13C-{1H} NMR (50.31 MHz, 293 K, CDCl3): δ 6.26 and 6.68 (d,
1
1JCP = 26.6, JCPЈ = 25.8, PCH3), 17.4–19.0 (m, PCH(CH3)2),
24.6, 25.8, 26.1 and 26.3 (d, PCH(CH3)2), 25.5 and 28.0 (s,
CH3COCHCOCH3), 100.2 (s, CH3COCHCOCH3), 185.8 and
2
188.0 (s, CH3COCHCOCH3) and 204.2 (t, JCP = 2JCPЈ = 17.2
Hz, CO).
Acknowledgements
We thank Dra. Ma Ángeles Aramendía, from the Depart-
amento de Química Orgánica, Universidad de Córdoba, for
mass spectrometry measurements. Financial support from the
Ministerio de Educación y Ciencia of Spain (DGICYT, Project
PB97-1357) and Junta de Andalucía (PAI-FQM 0188) is
gratefully acknowledged. We thank Johnson Matthey plc for
generous loans of ruthenium trichloride.
24 M. A. Queirós and S. D. Robinson, Inorg. Chem., 1978, 17, 310.
25 P. T. Beurskens, DIRDIF, Technical Report 1984/1, Crystallography
Laboratory, Toernooiveld, 1984.
26 TEXSAN, Single-Crystal Structure Analysis Software, version 5.0,
Molecular Structure Corporation, Houston, TX, 1989.
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