Structural studies of an array of mixed diamine phosphine ruthenium(II) complexes

Article abstract of DOI:10.1021/om0105831

Treatment of RuCl₂(η²-Ph₂PCH ₂CH₂OCH₃)₂ with various chelating diamines permitted the isolation of the corresponding RuCl₂(η ¹-Ph₂PCH₂

Full text of DOI:10.1021/om0105831

Organometallics 2002, 21, 105-112
105
Str u ctu r a l Stu d ies of a n Ar r a y of Mixed Dia m in e
P h osp h in e Ru th en iu m (II) Com p lexes1
Christiane Nachtigal, Samer Al-Gharabli, Klaus Eichele,
Ekkehard Lindner,* and Hermann A. Mayer*
Universita¨t Tu¨bingen, Institut fu¨r Anorganische Chemie, Auf der Morgenstelle 18,
72076 Tu¨bingen, Germany
Received J une 29, 2001
Treatment of RuCl2(η2-Ph2PCH2CH2OCH3)2 with various chelating diamines permitted
the isolation of the corresponding RuCl2(η1-Ph2PCH2CH2OCH3)2(diamine) complexes in high
yield (diamine ) 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-phen-
ylenediamine, 1,8-diaminonaphthalene, 2,2′-bipyridine, 1,10-phenanthroline). In solution,
all complexes prefer the trans-chloro cis-phosphine arrangement, as deduced by NMR
spectroscopy. X-ray studies showed that in the solid state all three possible isomers of the
octahedral RuCl2P2(diamine) complexes are present. The reaction of the RuCl2(η1-Ph2PCH2-
CH2OCH3)2(diamine) complexes with 1 equiv of AgSbF6, AgBF4, or TlPF6 leads to the
abstraction of one chloride by simultaneously coordinating one ether oxygen to ruthenium
and forming monocationic [RuCl(η1-Ph2PCH2CH2OCH3)(η2-Ph2PCH2CH2OCH3)(diamine)]+
compounds. If a large excess of silver or thallium salt is used, the dichloro complexes are
converted to the [Ru(η2-Ph2PCH2CH2OCH3)2(diamine)]2+ dications. In the case of 1,2-
phenylendiamine as coligand, the corresponding dication is only observed in traces. NMR
spectroscopic investigations and X-ray structural analyses confirm the η1 and η2 coordination
of the ether-phosphine ligands in the corresponding mono- and dicationic ruthenium(II)
complexes.
In tr od u ction
tures. Small differences in the coordination sphere of
the transition metal commonly lead to dramatic changes
in the selectivity and activity of the catalytic conver-
sion.13 Thus, the relation between the structure of the
ligands and the physicochemical properties of the cor-
responding metal complexes has been the subject of
many investigations in order to understand the selectiv-
ity in catalysis.
A prospective objective of our group is the combination
of parallel synthesis and interphase chemistry. As an
example, neutral and cationic diamine(ether-phos-
phine)ruthenium(II) complexes were selected. We have
successfully supported (ether-phosphine)ruthenium(II)
complexes on polysiloxane phases by the sol-gel
route14-18 and demonstrated their use as catalysts in
interphases.19,20 For the development of parallel and
screening methods for this chemistry, the (ether-
phosphine)ruthenium(II) complexes have to be modified
in order to create a large array of structurally different
The combinatorial approach as well as miniaturiza-
tion, automated parallel synthesis, and screening meth-
ods have become increasingly important in many areas
of chemistry.2-5 Besides the enormous gain in time in
the development of new drugs and catalysts, a further
driving force is the saving of expensive and environ-
mentally encumbering chemicals. While in drug design
there have already been a number of successful applica-
tions of these new techniques,6 in catalysis research
these new methods have been introduced only gradu-
ally.4,5,7 Many approaches to parallelization in catalysis
focus on screening methods.8-12 Highly selective cata-
lysts require transition-metal complexes with well-
designed structural, electronic, and stereochemical fea-
(1) Supported Organometallic Complexes. 29. Part 28: Hoehn, F.;
Lindner, E.; Mayer, H. A.; Hermle, T.; Rosenstiel, W. J . Chem. Inf.
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Chem. Soc. 1994, 116, 348.
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1994, 620, 1142.
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Mayer, H. A.; Benez, A.; Plies, E. Inorg. Chem. 1997, 36, 862.
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10.1021/om0105831 CCC: $22.00 © 2002 American Chemical Society
Publication on Web 12/04/2001

106 Organometallics, Vol. 21, No. 1, 2002
Nachtigal et al.
Sch em e 1
compounds. Thus, diamines which are easily accessible
in various forms were introduced as coligands. Di-
aminediphosphineruthenium(II) complexes with various
combinations of phosphine and diamine ligands have
been successfully developed21-30 to catalyze the hydro-
genation of ketones in the presence of carbon-carbon
multiple bonds with high diastereo- and enantioselec-
tivity.31-36
Here we wish to report on the validation of a synthetic
route to novel highly reactive bis(chelated) diamine-
(ether-phosphine)ruthenium(II) complexes and their
complete characterization by NMR and MS spectroscopy
and X-ray diffractometry. These complexes will serve
as benchmarks for parallel synthesized libraries of these
types of complexes.
Resu lts a n d Discu ssion
For the synthesis of the mixed diaminediphosphineru-
thenium(II) complexes 3-5 according to Scheme 1,
advantage was taken of the hemilabile character of the
ether-phosphine ligand Ph2PCH2CH2OCH3.37-39 This
route was found to be the most straightforward and
efficient way to generate the highly reactive products
5a -g. Moreover, this method is generally applicable to
numerous comparable examples and thus is promising
for later use in parallel synthesis. The hemilabile ether-
phosphines serve several purposes: (i) the coordinated
phosphines stabilize the complexes and increase the
electron density at the metal site (η1(P)-coordinated,
P∼O), (ii) the ether functions act as synthetic tools
during preparation of the diamine complexes 3a -g, and
(iii) the ether complexes act as protecting groups of the
reactive sites in the catalyst precursors 5a -g (η2(P,O)-
coordinated, PkO).40
(21) Noyori, R.; Ohkuma, T. Angew. Chem. 2001, 113, 40; Angew.
Chem., Int. Ed. 2001, 40, 40.
Ch a r t 1
(22) Tudor, M. D.; Becker, J . J .; White, P. S.; Gagne, M. R.
Organometallics 2000, 19, 4376.
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A. Org. Lett. 2000, 2, 4173.
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F.; Verdonck, L.; van Koten, G. J . Organomet. Chem. 2000, 603, 244.
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nometallics 1997, 16, 1401.
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M.; Uemura, S. J . Organomet. Chem. 1999, 572, 163.
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Commun. 1999, 2, 66.
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Dalton Trans. 1979, 1618.
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M.; Katayama, E.; England, A. F.; Ikariya, T.; Noyori, R. Angew. Chem.
1998, 110, 1792; Angew. Chem., Int. Ed. 1998, 37, 1703.
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38, 495.
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2001, 20, 1047.
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2000, 19, 2655.
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Soc. 1995, 117, 10417.
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S. H.; Wan, H. L.; Tsai, K. R.; Ikariya, T. J . Mol. Catal. A 1999, 147,
105.
(37) Lindner, E.; Schober, U.; Fawzi, R.; Hiller, W.; Englert, U.;
Wegner, P. Chem. Ber. 1987, 120, 1621.
(38) Lindner, E.; Mo¨ckel, A.; Mayer, H. A.; Ku¨hbauch, H.; Fawzi,
R.; Steimann, M. Inorg. Chem. 1993, 32, 1266.
(39) McCann, G. M.; Carvill, A.; Lindner, E.; Karle, B.; Mayer, H.
A. J . Chem. Soc., Dalton Trans. 1990, 3107.
Syn th esis a n d Ch a r a cter iza tion of th e Ru Cl2P 2-
(d ia m in e) Com p lexes 3a -g. The bis(ether-phos-
phine)ruthenium(II)37,39 complex 2 has two weak ru-
thenium-oxygen interactions which are easily cleaved
by the stronger nitrogen donors of bidentate diamine
ligands. Thus, mixing the bis-chelate 2 with a slight
excess of the diamines a -g in dichloromethane gives
the ruthenium(II) species RuCl2P2(diamine) (3a -g) in
good to very good yield (Scheme 1). The yellow (3a -d ),
brown (3e,f), and red (3g) solids are soluble in organic
solvents. For octahedral structures of the general for-
mula RuCl2P2(diamine) there are three possible coor-
dination geometries. NMR spectroscopy allows us to
distinguish between the isomers which are displayed
1
in Chart 1. In the H NMR spectra of RuCl2P2(diamine)
(3a -g), characteristic sets of signals are observed which
can be assigned to the phosphine as well as to the
diamine ligands. In all cases the broad and featureless
peaks prevent a detailed analysis; however, the integra-
tion of the proton resonances indicates that the phos-
(40) Slone, C. S.; Weinberger, D. A.; Mirkin, C. A. Prog. Inorg. Chem.
1999, 48, 233.

Mixed Diamine Phosphine Ruthenium(II) Complexes
Organometallics, Vol. 21, No. 1, 2002 107
phine-to-diamine ratio is in agreement with the com-
position of 3a -g. Furthermore, the chemical shifts of
the singlets due to the protons of the methoxy functions
agree well with the η1-P∼O unit. The singlets in the
31P{1H} NMR spectra of 3a ,b and 3d -g indicate that
the phosphine groups are chemically equivalent, which
is only the case if the structure of the RuCl2P2(diamine)
isomers has C2v symmetry, as in B or C (Chart 1). The
nonsymmetrical diamine in 3c causes the loss of the C2
axis, which results in the splitting of the phosphorus
resonances into an AB pattern. For compounds 3d ,f,
additional AX multiplets are observed in the 31P{1H}
NMR spectra. These signals are generated from minor
amounts of the C1-symmetrical cis,cis,cis-RuCl2P2-
(diamine) isomers (structure A), which are also formed
during the reaction. The phosphorus chemical shifts of
3a -g and the phosphorus-phosphorus coupling con-
stants of 3c suggest that the ether-phosphines are η1-
(P)-coordinated37,39 and are positioned cis to one another.
Given also the presence of the diamine chelate, the
chlorines have to be in a mutually trans arrangement.
This supports structure B as the most favored geometry
in solution. The 13C{1H} NMR spectra are consistent
with these findings. Characteristic signals are found due
to the η1(P)-ether-phosphines as well as due to the
aliphatic (3a -c) and aromatic diamines (3d -g). In the
13C{1H} NMR spectra of complexes 3a ,b,d -g the AXX′
splitting patterns which are observed for the carbon
atoms attached to phosphorus are caused by the inter-
action of the magnetically inequivalent phosphorus
atoms with the 13C nuclei. They are also compatible with
structure B (Chart 1).
While geometry B is preferred in solution, all three
structures A-C (Chart 1) are found in the solid state.
This was confirmed by single-crystal X-ray diffraction
studies of the complexes 3a -c,e,g. Examples for struc-
ture A (3a ) and B (3e) are shown in Figure 1, and
selected bond distances and angles are summarized in
Table 1. The 1,3-diaminopropane (3b),41 1,2-diamino-
propane (3c),41 and 1,8-diaminonaphthaline (3e) (Figure
1) derivatives crystallize in the coordination geometry
B, which represents the most commonly found structure
for mixed-ligand ruthenium complexes of this type.21
Rarely observed is the cis,cis,cis form A, which is favored
by the 1,2-diaminoethane complex 3a (Figure 1), and
the geometry C, where the phosphines are located
mutually trans to each other as in the 1,10-phenan-
throline complex 3g. Unfortunately, the quality of the
crystal of 3g was so poor that, besides the arrangements
of the ligands around ruthenium, no further information
can be given with respect to bond lengths and angles.
Cr ysta l Str u ctu r es of 3a a n d 3e. In 3a , the all-cis
isomer A (Chart 1), the octahedral coordination of
ruthenium is slightly distorted, the equatorial plane
consisting of the atoms Cl(2), P(1), N(1), and N(2) being
displaced toward the sterically less demanding Cl(1)
such that Ru(1) is shifted out of this plane toward P(2)
by almost 0.2 Å. This is also reflected in the fact that
most of the angles formed by Cl(1) with ligands in cis
positions are significantly smaller than 90°, with the
Cl(1)-Ru(1)-Cl(2) angle of 92.86(6)° being the ex-
ception. In contrast, the Cl(1)-Ru(1)-P(2) angle be-
tween the axial ligands, 174.49(6)°, deviates moderately
F igu r e 1. ORTEP plots of (a) 3a and (b) 3e shown at the
50% probability level. Hydrogen atoms are omitted for
clarity.
from a linear arrangement. The different trans influ-
ences of the ligands at ruthenium affects the Ru-P
distances only marginally, with Ru(1)-P(1) (2.296(2) Å,
trans to nitrogen) slightly longer than Ru(1)-P(2)
(2.244(2) Å, trans to chlorine). The methoxyethyl chains
of both phosphine ligands implement all-trans confor-
mations, with torsional angles being in the range of
171-176°. The 1,2-diaminoethane chelate adopts a
twist conformation, with C(10) and C(11) twisted out
of the plane formed by Ru(1), N(1), and N(2) by 0.4 and
-0.2 Å.
In 3e, the more common isomer B (Chart 1), the
atoms Ru(1), P(1), P(2), N(1), and N(2) deviate by less
than 0.08 Å from the equatorial least-squares plane.
However, the chlorine atoms are pushed from their axial
positions toward the diamine by the phosphine ligands,
(41) Eichele, K.; Nachtigal, C. Unpublished results.

108 Organometallics, Vol. 21, No. 1, 2002
Nachtigal et al.
Ta ble 1. Selected Bon d Len gth s (Å) a n d Bon d
An gles (d eg) for 3a ,e, 4b, a n d 5a
ing to groups which are directly bound to the ruthenium-
coordinated oxygen. Thus, chemical shift differences of
1
3-6 ppm in the 13C{1H} and of 0.1-0.5 ppm in the H
3a
3e
4b
5a
NMR spectra are observed for the CH2OCH3 fragments.
Ru(1)-Cl(1)
Ru(1)-Cl(2)
Ru(1)-P(1)
Ru(1)-P(2)
Ru(1)-N(1)
Ru(1)-N(2)
Ru(1)-O(1)
Ru(1)-O(2)
2.488(2)
2.436(2)
2.296(2)
2.244(2)
2.147(5)
2.134(5)
2.420(1)
2.416(1)
2.275(1)
2.272(1)
2.211(2)
2.208(2)
2.412(1)
2
The 31P{1H} NMR spectra contain AX patterns with J PP
2.307(1)
2.248(1)
2.178(3)
2.148(3)
2.309(2)
2.304(2)
2.234(2)
2.184(7)
2.122(7)
2.283(7)
2.182(6)
coupling constants typically found for cis-arranged
phosphines.
The loss of symmetry which is caused by the 2-fold
ring closure in 5a -c,e-g results in two chemically
inequivalent phosphine groups. As they are located in
similar structural environments, their 31P{1H} NMR
spectra display the typical splitting patterns of AB
spectra. The small coupling constants (2J PP ≈ 35 Hz)
confirm the cis arrangement of both phosphine groups
in the complexes 5a -c,e-g. The chiral carbon center
in the diamine ligand of 5c generates a pair of dia-
stereomeric complexes, which give rise to two AB
multiplets in the 31P{1H} NMR spectrum. The ad-
ditional low-field shifts of the 31P resonances in the
spectra of 5a -c,e-g compared to those of 3a -g are
indicative of the formation of five-membered rings.42
This is supported by the 13C{1H} NMR spectra. Due to
the coordination of the ether oxygen, the 13C signals of
the carbon atoms of the methyl and methylene groups
bound to the oxygen are shifted to lower field by
approximately 10 ppm. In agreement with the 31P{1H}
NMR spectra, two sets of signals are observed in the
13C{1H} NMR spectra of 5a -c,e-g for the phosphine
ligands. The spectra are completed by the characteristic
13C resonances of the diamines in the alkane (5a -c)
and aromatic (5e-f) regions, respectively.
Cr ysta l Str u ctu r es of 4b a n d 5a . The cationic
complex 4b shares some structural features with the
isomer A of complex 3a , insofar as one phosphine ligand
is located in the equatorial plane defined by the chelat-
ing diamine ligand, while the other phosphine ligand
resides in an axial position (Figure 2). Consequently,
the ruthenium is displaced from the equatorial plane
toward P(2) by 0.17 Å and the angles involving O(1) and
cis ligands are significantly smaller than 90°. The
diaminopropane chelate adopts a chair conformation,
where the tip involving ruthenium is flattened (torsional
angles about the Ru-N bonds are 19-22°) but C(11) is
pushed more strongly out of plane (torsional angles
about the C(11)-C(10) and C(11)-C(12) bonds in the
range 71-74°). The five-membered chelate created by
the η2-phosphine forms a regular twisted ring. The two
Ru-P distances differ from each other more than in the
neutral compounds 3a ,e. The methoxyethyl chain of the
η1-phosphine is in an all-trans conformation, except for
the P-C bond that adopts a gauche position with
respect to the chain, with a P-C-C-O torsional angle
of 71°.
Cl(1)-Ru(1)-Cl(2) 92.86(6)
167.56(2)
Cl(1)-Ru(1)-N(1) 80.02(15) 81.81(6)
Cl(1)-Ru(1)-N(2) 80.05(15) 82.44(6)
79.97(8)
165.67(8)
98.86(3)
93.45(3)
98.63(4)
90.1(1)
88.5(1)
80.7(1)
81.08(7)
177.89(7) 171.5(2)
90.1(3)
Cl(1)-Ru(1)-P(1) 86.73(6)
90.80(3)
Cl(1)-Ru(1)-P(2) 174.49(6) 97.39(3)
P(1)-Ru(1)-P(2)
97.61(6)
92.50(3)
75.4(1)
95.45(8)
80.3(3)
90.7(3)
86.7(3)
81.00(18)
N(1)-Ru(1)-N(2) 80.2(2)
O(1)-Ru(1)-N(1)
O(1)-Ru(1)-N(2)
P(1)-Ru(1)-O(1)
P(2)-Ru(1)-O(1)
O(2)-Ru(1)-N(1)
O(2)-Ru(1)-N(2)
P(1)-Ru(1)-O(2)
P(2)-Ru(1)-O(2)
O(1)-Ru(1)-O(2)
169.7(3)
88.97(18)
82.43(18)
89.7(3)
forming an angle of 167.56(2)°. The plane of the di-
amine ligand is tilted from the equatorial plane by a
dihedral angle of 42.8(1)°. In comparison to 3a , the
Ru-Cl distances are slightly shorter and the Ru-N
bonds slightly longer. In the methoxyethyl chains of
the phosphines, the P-C bonds deviate from an all-
trans arrangement and, with P-C-C-O torsional
angles of 151 and 144°, are almost partially eclipsed
(anticlinal).
Syn th eses a n d Ch a r a cter iza tion of th e Ca tion s
[Ru Cl(P ∼O)(P kO)(NkN)]X (4a -d ,f) a n d [Ru (P kO)2-
(NkN)]X2 (5a -c,e-g). Complexes 3a -g react with
different chloride scavengers such as AgSbF6, AgBF4,
and TlPF6 in dichloromethane to give solutions from
which the mono- and dicationic salts 4a -d ,f, and
5a -c,e-g are isolated (Scheme 1). Depending on the
amount of silver and thallium salt used, one or two
chloride ions are abstracted by simultaneously closing
one or two rings via ether coordination. In the case of
3d , the conversion into 5d remained incomplete, even
after a prolonged reaction time and the presence of a
large excess of silver salt. Only traces of 5d are observed
in addition to the main product 4d . In these reaction
steps, the advantage of the ether-phosphines becomes
obvious, as they protect the vacant coordination sites
and circumvent the need for further weakly coordinating
ligands such as acetonitrile, THF, and acetone. The
mono- and dicationic species 4a -d ,f, and 5a -c,e-g are
obtained as colored powders. In the solid state they are
relatively insensitive, while in solution they are rather
sensitive toward air. They readily decompose in the
presence of water. Due to their polar composition they
dissolve in moderately polar solvents such as dichlo-
romethane.
In the dicationic complex 5a , the phosphorus atoms
differ also with respect to the equatorial plane defined
by the chelating 1,2-diaminoethane. However, the out-
of-plane displacement of ruthenium toward P(2) is not
as strong (0.12 Å). Similar to 4b, the η2-phosphine
chelate involving P(1) adopts a twist conformation, as
does the ethylenediamine ring. In contrast, the η2-
phosphine involving P(2) adopts an envelope conforma-
tion, with C(6) forming the flap.
The formation of only one η2-PkO chelate ring gener-
ates two sets of resonances in the 1H, 13C{1H}, and
31P{1H} NMR spectra of the monocationic complexes
4a -d ,f. In all cases, the signals caused by the ether-
phosphine chelate are shifted downfield compared to the
η1-P∼O unit. This holds especially for the nuclei belong-
(42) Lindner, E.; Fawzi, R.; Mayer, H. A.; Eichele, K.; Hiller, W.
Organometallics 1992, 11, 1033.

Mixed Diamine Phosphine Ruthenium(II) Complexes
Organometallics, Vol. 21, No. 1, 2002 109
transformation of this chemistry to automatization and
parallelization is in progress.
Exp er im en ta l Section
Gen er a l Com m en ts. All experiments were carried out
under an atmosphere of argon by use of standard Schlenk
techniques. Solvents were dried with appropriate reagents,
distilled, degassed, and stored under argon.
RuCl3‚3H2O was purchased from ChemPur; 1,8-diamino-
naphthalene and AgSbF6 were available from Fluka. AgBF4,
1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane,
1,2-phenylenediamine, 2,2′-bipyridine, 1,10-phenanthroline,
and TlPF6 were purchased from Merck or Strem.
The precursor RuCl2(PPh3)3,43 the ether-phosphine Ph2P-
(CH2)2OCH3,44 and 237 were synthesized according to literature
methods.
Elemental analyses were performed with an Elemental
Vario EL analyzer. FD mass spectra were taken on a Finnigan
MAT 711 A instrument, modified by AMD and reported as
mass/charge (m/z). The high-resolution 31P{1H} and 13C{1H}
NMR spectra were recorded on a Bruker DRX 250 spectrom-
eter at 298 K. Frequencies and standards are as follows:
31P{1H} NMR, 101.25 MHz; 13C{1H} NMR, 62.90 MHz. The
1H and 13C chemical shifts were calibrated to deuterated
solvent peaks, which are reported relative to TMS. All assign-
ments are supported by 13C 135DEPT experiments. 31P chemi-
cal shifts were measured relative to 85% H3PO4 (δ 0).
Gen er a l P r oced u r e for th e P r ep a r a tion of th e Neu tr a l
Com p lexes 3a -g. The corresponding dinitrogen ligand a -g
(10% excess) was dissolved in 25 mL of dichloromethane and
added dropwise to a stirred solution of 2 in 25 mL of di-
chloromethane. After the reaction mixture had been stirred
for another 45 min at room temperature, the volume of the
solution was concentrated to about 5 mL under reduced
pressure. Addition of 80 mL of n-hexane caused the precipita-
tion of a solid, which was filtered off (P3), washed three times
with 25 mL portions of n-hexane, and dried under vacuum.
Com p lex 3a . Complex 2 (300 mg, 0.454 mmol) was treated
with a (0.033 mL, 0.50 mmol) to give 3a : yield 307 mg (94%)
of a yellow powder. 1H NMR (CDCl3): δ 2.2-2.4 (m, 4H, PCH2),
2.6-2.8 (m, 8H, CH2NH2), 2.9 (s, 6H, OCH3), 2.9-3.0 (m, 4H,
CH2O), 7.1-7.7 (m, 20H, C6H6). 31P{1H} NMR (CDCl3): δ 38.8
(s). 13C{1H} NMR (CDCl3): δ 25.2 (m,45a N ) 27.0 Hz, PCH2),
43.6 (s, NCH2), 57.9 (s, OCH3), 69.0 (s, CH2O), 128.2 (m,45b
N
F igu r e 2. ORTEP plots of (a) 4b and (b) 5a shown at the
50% probability level. Hydrogen atoms are omitted for
clarity.
) 8.2 Hz, m-C6H5), 129.1 (s, p-C6H5), 132.7 (m,45c N ) 8.2 Hz,
o-C6H5), 134.4 (m,45a N ) 35 Hz, i-C6H5). FD-MS: m/z 720.6
(M+). Anal. Calcd for C32H42Cl2N2O2P2Ru: C, 53.34; H, 5.87;
N, 3.89; Cl, 9.84. Found:25 C, 52.87; H, 5.53; N, 3.71; Cl, 9.87.
Com p lex 3b. Compound 2 (300 mg, 0.454 mmol) was
treated with b (0.042 mL, 0.50 mmol) to give 3b: yield 320
Con clu sion
An efficient method to produce a large variety of
neutral and cationic diamine(ether-phosphine)ruthe-
nium(II) complexes was established. The geometry of
these complexes is controlled via the cis diamines and
the ether-phosphine ligands. Of importance is the
exclusive cis arrangement of the weak Ru-O bonds in
the complexes 5a -c,e-g, since many of the transition-
metal-catalyzed conversions require two available co-
ordination sites cis to one another. Interestingly, in the
case of the neutral complexes 3a -g without Ru-O
contacts, a sensitive interplay between the stereochem-
istry of the diamine ligand and electronic factors decide
the geometry of the complex. Therefore, all three pos-
sible isomers are found in the solid state by X-ray
analysis of the complexes 3a -g. However, as catalysis
is performed in solution or under solution-like condi-
tions, this should have no impact on the selectivity and
activity of the potential catalyst precursors 3a -g, since
in solution geometry B is exclusively formed. The
1
mg (96%) of a yellow powder. H NMR (CDCl3): δ 1.6 (m, 2H,
NCH2CH2), 2.2-2.4 (m, 4H, PCH2), 2.9 (s, 6H, OCH3),
2.8-3.0 (m, 12H, NH2CH2, CH2O), 7.2-7.7 (m, 20H, C6H5).
31P{1H} NMR (C6D6): δ 42.7 (s). 13C{1H} NMR (C6D6): δ 26.8
(m,45a N ) 28.0 Hz, PCH2), 29.9 (s, NCH2CH2), 39.5 (s, NCH2),
58.0 (s, OCH3), 70.0 (s, CH2O), 128.6 (m,45b N ) 7.6 Hz,
m-C6H5), 129.6 (s, p-C6H5), 134.0 (m,45c N ) 7.2 Hz, o-C6H5),
134.6 (m,45a N ) 32.7 Hz, i-C6H5). FD-MS: m/z 734.6 (M+).
Anal. Calcd for C33H44Cl2N2O2P2Ru: C, 53.95; H, 6.04; N, 3.81;
Cl, 9.65. Found:46 C, 53.29; H, 6.15; N, 3.58; Cl, 9.32.
(43) Stephenson, T. A.; Wilkinson, G. J . Inorg. Nucl. Chem. 1966,
28, 945.
(44) Lindner, E.; Meyer, S.; Wegner, P.; Karle, B.; Sickinger, A.;
Steger, B. J . Organomet. Chem. 1987, 335, 59.
1
3
(45) A part of an AXX′ pattern: (a) N ) | J PC
+
3J PC|; (b) N ) | J PC
2
+
5J PC|; (c) N ) | J PC
+
4J PC|.
(46) Although high temperature and catalyst was used to determine
the C, H analyses, some of the carbon values remained low. This is
probably due to incomplete combustion, which may be caused by
ruthenium.

110 Organometallics, Vol. 21, No. 1, 2002
Nachtigal et al.
Com p lex 3c. Complex 2 (300 mg, 0.454 mmol) was treated
with c (0.043 mL, 0.50 mmol) to give 3c: yield 304 mg (91%)
of a yellow powder. 1H NMR (CDCl3): δ 0.9 (d, 3J HH ) 4.5 Hz,
3H, CHCH3), 1.9-2.2 (m, 1H, CHCH3), 2.4-3.3 (m, 14H, PCH2,
CH2O, NH2, NH2CH2), 2.9 (br, 6H, OCH3), 7.2-7.8 (m, 20H,
was added to a solution of the neutral complexes 3a -g in 25
mL of dichloromethane and stirred for 24 h. After filtration
through silica the solution was concentrated to about 5 mL
under reduced pressure. The corresponding cationic complex
was precipitated by addition of 100 mL of diethyl ether, filtered
off (P3), washed three times with 25 mL portions of diethyl
ether, and dried under vacuum.
Use of AgBF 4. A solution of AgBF4 (5% excess) in 25 mL of
dichloromethane was added to a solution of the neutral
complexes 3a -g in 25 mL of dichloromethane and stirred for
4 h. After filtration through silica the solution was concen-
trated to a small volume. Adding 100 mL of diethyl ether
caused the precipitation of a solid, which was filtered off (P3),
washed three times with 25 mL portions of diethyl ether, and
dried under vacuum.
2
C6H5). 31P{1H} NMR (CDCl3): δ 39.1, 38.9 (AB pattern, J PP
) 36.7 Hz). 13C{1H} NMR (CDCl3): δ 20.4 (s, CCH3), 25.4 (m,
PCH2), 49.6 (s, NCH), 50.9 (s, NCH2), 58.0 (s, OCH3), 69.1 (d,
3
2J PC ) 4.0 Hz, CH2O), 128.1 (d, J PC ) 4.9 Hz, m-C6H5), 128.2
3
(d, J PC ) 6.4 Hz, m-C6H5), 129.0, 129.3 (2s, p-C6H5), 132.3,
2
133.2 (2d, J PC ) 6.4 Hz, o-C6H5), 134.8-133.8 (m, i-C6H5).
FD-MS: m/z 734.6 (M+). Anal. Calcd for C33H44Cl2N2O2P2Ru:
C, 53.95; H, 6.04; N, 3.81; Cl, 9.65. Found: C, 53.53; H, 5.75;
N, 3.75; Cl, 9.38.
Com p lex 3d . Complex 2 (300 mg, 0.454 mmol) was treated
with d (54 mg, 0.50 mmol) to give 3d : yield 206 mg (59%) of
a pale yellow powder. 1H NMR (CDCl3): δ 2.2-2.4 (m, 4H,
PCH2), 2.9 (m, 6H, OCH3), 2.9-3.0 (m, 4H, CH2O), 4.5 (s, 4H,
NH2), 6.8-7.0 (m, 4H, C6H4), 7.1-7.7 (m, 20H, C6H5). 31P{1H}
NMR (CDCl3): δ 40.7 (s). 13C{1H} NMR (CDCl3): δ 25.2 (m,45a
N ) 26.5 Hz, PCH2), 58.0 (s, OCH3), 69.1 (m,45b N ) 5.0 Hz,
CH2O), 127.3 (s, C3, C6), 127.8 (s, C4, C5), 128.4 (m,45b N )
8.5 Hz, m-C6H5), 129.4 (s, p-C6H5), 132.8 (m,45c N ) 8.4 Hz,
o-C6H5), 134.2 (m,45a N ) 36.3 Hz, i-C6H5), 140.1 (s, C1, C2).
31P{1H} NMR (CDCl3) for the C1 isomer: δ 37.6 (d, 2J PP ) 34.9
Com p lex 4a . Complex 3a (300 mg, 0.416 mmol) was treated
with TlPF6 (153 mg, 0.437 mmol) to give 4a : yield 252 mg
(73%) of a yellow powder. 1H NMR (CD2Cl2): δ 0.9-1.5 (m,
2H, CH2P), 2.1-2.8 (m, 10H, CH2NH2, CH2P), 2.9 (s, 3H,
OCH3), 2.9-3.1 (m, 2H, CH2O), 3.6 (s, 3H, OCH3), 3.7-4.0 (m,
2H CH2O), 6.5-8.1 (m, 20H, C6H5). 31P{1H} NMR (CD2Cl2): δ
57.5 (d, 2J PP ) 37.8 Hz), 48.5 (d, 2J PP ) 37.8 Hz), -143.3 (sept,
1J PF ) 712.1 Hz, PF6-). 13C{1H} NMR (CD2Cl2): δ 28.6 (d, 1J PC
1
) 28.5 Hz, PCH2), 32.2 (d, J PC ) 25.6 Hz, PCH2), 43.7, 45.5
(2s, NCH2), 58.5, 61.3 (2s, OCH3), 68.6, 73.9 (2s, CH2O), 128.6
2
Hz), 47.5 (d, J PP ) 34.9 Hz). FD-MS: m/z 768.7 (M+), 660.5
(d, 3J PC ) 10.0 Hz, m-C6H5), 129.1(d, 3J PC ) 10.0 Hz, m-C6H5),
(M+ - C6H8N2). Anal. Calcd for C36H42Cl2N2O2P2Ru: C, 56.25;
H, 5.51; N, 3.64; Cl, 9.22. Found:46 C, 55.64; H, 5.97; N, 3.82;
Cl, 8.94.
3
3
129.9 (d, J PC ) 10.0 Hz, m-C6H5), 130.0 (d, J PC ) 10.0 Hz,
2
m-C6H5), 130.8-130.9 (br, p-C6H5), 131.6 (d, J PC ) 9.0 Hz,
2
2
o-C6H5), 131.9 (d, J PC ) 9.0 Hz, o-C6H5), 133.0 (d, J PC
)
1
Com p lex 3e. Compound 2 (300 mg, 0.454 mmol) was
treated with e (79 mg, 0.50 mmol) to give 3e: yield 299 mg
(84%) of a tawny powder. 1H NMR (CDCl3): δ 2.3-2.4 (m, 4H,
PCH2), 2.9 (s, 6H, OCH3), 2.9-3.1 (m, 4H, CH2O), 5.1 (s, 4H,
NH2), 6.4-7.5 (m, 6 H, C10H6), 7.3-7.7 (m, 20H, C6H5).
31P{1H} NMR (CD2Cl2): δ 43.9 (s). 13C{1H} NMR (CD2Cl2): δ
25.7 (m,45a N ) 26.3 Hz, PCH2), 58.2 (s, OCH3), 69.5 (s, CH2O),
121.7 (s, C2, C7), 125.2 (s, C8a), 126.0 (s, C4, C5), 126.9 (s,
C3, C6), 128.8 (m,45b N ) 8.5 Hz, m-C6H5), 129.8 (s, p-C6H5),
9.0 Hz, o-C6H5), 134.1 (d, J PC ) 44.1 Hz, i-C6H5), 135.1 (d,
2J PC ) 10.0 Hz, o-C6H5), 138,1 (d, J PC ) 37.7 Hz, i-C6H5).
1
FD-MS: m/z 685.2 (M+ - PF6). Anal. Calcd for C32H42
-
ClF6N2O2P3Ru: C, 46.30; H, 5.10; N, 3.37. Found: C, 45.92;
H, 5.37; N, 3.39.
Com p lex 4b. Complex 3b (300 mg, 0.408 mmol) was treated
with TlPF6 (150 mg, 0.429 mmol) to give 4b: yield 238 mg
(69%) of a yellow powder. 1H NMR (CD2Cl2): δ 0.6-4.2 (br m,
16H, CH2P, H2NCH2CH2CH2NH2, CH2O), 2.9, 3.8 (2s, 6H,
OCH3), 6.3-8.2 (m, 20H, C6H5). 31P{1H} NMR (CD2Cl2): isomer
133.7 (m,45c N ) 7.8 Hz, o-C6H5), 134.2 (s, C4a), 136.1 (m,45a
N
) 44.8 Hz, i-C6H5), 136.8 (s, C1, C8). FD-MS: m/z 783.3 (M+
- Cl), 660.5 (M+ - C10H10N2). Anal. Calcd for C40H44Cl2N2O2P2-
Ru: C, 58.68; H, 5.42; N, 3.42; Cl, 8.66. Found:46 C, 57.89; H,
5.43; N, 3.52; Cl, 9.03.
2
2
a (94%), δ 54.3 (d, J PP ) 36.5 Hz), 47.8 (d, J PP ) 36.5 Hz),
-143.3 (sept, 1J PF ) 711.8 Hz, PF6-); isomer b (6%), δ 63.4 (d,
2J PP ) 32.4 Hz), 32.4 (d, J PP ) 32.4 Hz), -143.3 (sept, J PF
)
2
1
711.8 Hz, PF6-). 13C{1H} NMR (CD2Cl2): isomer a, δ 27.5 (d,
1J PC ) 27.5 Hz, PCH2), 28.8 (s, NCH2CH2), 30.8 (d, 1J PC ) 26.0
Hz, PCH2), 41.4, 43.1 (2s, NCH2), 58.3, 61.7 (2s, OCH3), 68.2,
Com p lex 3f. Complex 2 (300 mg, 0.454 mmol) was treated
with f (78 mg, 0.50 mmol) to give 3f: yield 323 mg (87%) of a
1
3
auburn powder. H NMR (CDCl3): δ 2.5-2.6 (m, 4H, PCH2),
74.0 (2s, CH2O), 128.7 (d, J PC ) 9.2 Hz, m-C6H5), 129.2 (d,
2.8 (s, OCH3), 2.8-3.0 (m, 4H, CH2O), 6.6-8.7 (m, 28H, C10H8,
C6H5). 31P{1H} NMR (CDCl3): δ 30.5 (s). 13C{1H} NMR
(CDCl3): δ 26.8 (m,45a N ) 29.1 Hz, PCH2), 57.8 (s, OCH3),
69.4 (s, CH2O), 122.2 (s, C4, C4′), 123.9 (s, C6, C6′), 128.0 (m,45b
N ) 8.5 Hz, m-C6H5), 129.3 (s, p-C6H5), 133.3-134.1 (m, i-C6H5,
o-C6H5), 136.0 (s, C5, C5′), 156.6 (s, C3, C3′), 158.7 (s, C1, C1′).
31P{1H} NMR (CDCl3) for the C1 isomer: δ 29.3 (d, 2J PP ) 30.2
3J PC ) 9.0 Hz, m-C6H5), 130.1 (br, m-C6H5), 131.0 (br, p-C6H5),
2
131.2 (br, p-C6H5), 132.0 (d, J PC ) 8.0 Hz, o-C6H5), 132.4 (d,
2J PC ) 8.0 Hz, o-C6H5), 133.3 (d, J PC ) 9.0 Hz, o-C6H5), 134.9
2
2
1
(d, J PC ) 9.0 Hz, o-C6H5), 136.2 (d, J PC ) 41.0 Hz, i-C6H5).
FD-MS: m/z 699.2 (M+ - PF6). Anal. Calcd for C33H44
-
ClF6N2O2P3Ru: C, 46.95; H, 5.25; N, 3.32. Found: C, 47.27;
H, 4.95; N, 3.31.
2
Hz), 33.4 (d, J PP ) 30.2 Hz). FD-MS: m/z 816.7 (M+). Anal.
Com p lex 4c. Compound 3c (300 mg, 0.408 mmol) was
treated with AgBF4 (83 mg, 0.429 mmol) to give 4c: yield 218
mg (68%) of a yellow powder. 1H NMR (CD2Cl2): δ 0.4-4.3
(m, 33H, CH2P, H2NCH2CHNH2, CH2O), 0.8 (d, 2J HH ) 6.3 Hz,
Calcd for C40H42Cl2N2O2P2Ru: C, 58.83; H, 5.18; N, 3.43; Cl,
8.68. Found:46 C, 58.14; H, 5.32; N, 3.52; Cl, 8.69.
Com p lex 3g. Compound 2 (300 mg, 0.454 mmol) was
treated with g (90 mg, 0.50 mmol) to give 3g: yield 351 mg
2
3H, CHCH3), 1.1 (d, J HH ) 6.6 Hz, 6H, CHCH3), 3.0 (s, 3H,
1
(92%) of a deep red powder. H NMR (CDCl3): δ 2.5-2.7 (m,
OCH3), 3.1 (s, 6H, OCH3), 3.6 (s, 3H, OCH3), 3.7 (s, 6H, OCH3),
4H, PCH2), 2.8 (s, OCH3), 2.8-3.0 (m, CH2O), 7.0-9.0 (m, 28H,
C6H5, C12H8). 31P{1H} NMR (CDCl3): δ 30.5 (s). 13C{1H} NMR
(CDCl3): δ 26.7 (m,45a N ) 29.2 Hz, PCH2), 57.6 (s, OCH3),
69.2 (s, CH2O), 123.1 (s, C3, C8), 126.8 (s, C5, C6), 127.8 (m,45b
N ) 8.5 Hz, m-C6H5), 129.1 (s, p-C6H5), 130.0 (s, C4a, C6a),
133.4 (m,45a N ) 34.2 Hz, i-C6H5), 134.1 (br m,45c o-C6H5), 135.1
(s, C4, C7), 149.2 (s, C10a, C10b), 156.0 (s, C2, C9). FD-MS:
m/z 840.7 (M+). Anal. Calcd for C42H42Cl2N2O2P2Ru: C, 60.00;
H, 5.03; N, 3.33; Cl, 8.43. Found:46 C, 59.36; H, 5.34; N, 3.64,
Cl, 8.69.
6.2-8.3 (m, 20H, C6H5). 31P{1H} NMR (CD2Cl2): isomer a
2
2
(55%), δ 59.1 (d, J PP ) 37.2 Hz), 48.2 (d, J PP ) 37.2 Hz);
2
2
isomer b (25%), δ 57.6 (d, J PP ) 37.2 Hz), 47.8 (d, J PP ) 37.2
2
2
Hz); isomer c (20%), δ 56.8 (d, J PP ) 36.3 Hz), 49.9 (d, J PP
)
36.3 Hz). 13C{1H} NMR (CD2Cl2): δ 18.2, 18.6, 20.0 (3s,
CHCH3), 30.0-32.6 (m, PCH2), 51.2 (br, NCH2), 52.2 (br,
NCH), 58.7, 60.7, 61.0 (3s, OCH3), 68.8, 68.9, 73.8 (3s, CH2O),
128.4-137.0 (C6H5). FD-MS: m/z 699.2 (M+ - BF4). Anal.
Calcd for C33H44BClF4N2O2P2Ru: C, 50.43; H, 5.64; N, 3.56.
Found: C, 49.97; H, 5.73; N, 3.32.
Gen er a l P r oced u r e for th e P r ep a r a tion of th e Mon o-
ca tion ic Com p lexes 4a -c,f. Use of TlP F 6. TlPF6 (5% excess)
Com p lex 4d . Compound 3d (300 mg, 0.390 mmol) was
treated with AgBF4 (79 mg, 0.410 mmol) to give 4d : yield 337

Mixed Diamine Phosphine Ruthenium(II) Complexes
Organometallics, Vol. 21, No. 1, 2002 111
Ta ble 2. Cr ysta l Da ta a n d Su m m a r y of Da ta Collection a n d Refin em en t for 3a ,e, 4b, a n d 5a
3a ‚0.5C7H8
3e‚CH2Cl2
4b(PF6)
5a (SbF6)2
formula
C32H42Cl2N2O2P2Ru‚
0.5C7H8
C40H44Cl2N2O2P2Ru‚
CH2Cl2
C33H44ClF6N2O2P3Ru
C32H42F12N2O2P2RuSb2
fw
766.65
903.61
844.13
1121.19
cryst size, mm3
temp, K
cryst class
space group
a, Å
0.3 × 0.2 × 0.1
0.3 × 0.2 × 0.2
0.1 × 0.1 × 0.1
0.3 × 0.2 × 0.1
173(2)
173(2)
173(2)
173(2)
monoclinic
C2/c (No. 15)
31.03(1)
13.108(7)
18.054(4)
triclinic
P1h (No. 2)
9.492(2)
13.070(3)
16.724(5)
90.03(2)
93.62(2)
99.65(1)
2041.1(9)
2
1.470
0.762
928
monoclinic
P21/c (No. 14)
13.730(3)
11.869(4)
23.342(3)
106.52(1)
orthorhombic
Pbca (No. 61)
15.348(5)
15.163(6)
34.98(1)
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
100.44(2)
7221(5)
8
1.410
0.704
3176
3647(2)
4
1.537
0.698
1728
8141(5)
8
1.830
1.849
4384
Z
d
calcd, g/cm3
µ, mm-1
F(000)
θ range, deg
2.11-24.98
- 1 e h e 36
- 1 e k e 15
-21 e l e 21
7295
2.01-27.50
- 1 e h e 12
-16 e k e 16
-21 e l e 21
11 036
2.03-24.99
- 1 e h e 16
- 1 e k e 14
-27 e l e 27
8022
2.22-27.51
-1 e h e 19
-1 e k e 19
-1 e l e 45
11 052
index ranges
no. of data collected
Rint
0.0489
0.0665
0.0296
0.0508
no. of unique data/
restraints/params
GOF on F2
6285/10/385
9345/0/470
6399/0/434
9320/0/479
1.771
1.845
1.614
1.936
R1, wR2 (I > 2σ(I))a
R1, wR2 (all data)
largest diff peak, hole, e/Å3
0.0551, 0.1380
0.0830, 0.1606
1.204, -1.450
0.0402, 0.1007
0.0456, 0.1064
1.520, -1.129
0.0406, 0.0982
0.0488, 0.1061
2.748, -0.727
0.0602, 0.1387
0.1183, 0.1764
1.103, -1.259
R1 ) ∑(||Fo| - |Fc||)/∑|Fo|; wR2 ) [∑[w(Fo - Fc2)2]/∑[w(Fo2)2]]0.5; w ) [exp(5(sin2 θ)/λ2)]/[σ2(Fo2) + bP + (aP)2]; P ) [Fo + 2Fc2]/3.
a
2
2
mg (92%) of a dark brown powder which was contaminated
with traces of 5d . 1H NMR (CD2Cl2): δ 2.1-4.6 (m, 12H, CH2P,
CH2O, NH2), 3.1 (s, 3H, OCH3), 3.9 (s, 3H, OCH3), 6.4-7.8 (m,
Anal. Calcd for C32H42B2F8N2O2P2Ru: C, 46.68; H, 5.14; N,
3.40. Found: C, 47.00; H, 4.79; N, 3.42.
Com p lex 5b. Complex 3b (300 mg, 0.408 mmol) was treated
with TlPF6 (428 mg, 1.225 mmol) to give 5b: yield 265 mg
(68%) of a yellow powder. 1H NMR (CD2Cl2): δ 1.0-4.5 (m,
18H, PCH2, H2NCH2CH2CH2NH2, CH2O), 3.5, 4.0 (2s, 6H,
OCH3), 6.4-8.0 (m, 20H, C6H5). 31P{1H} NMR (CD2Cl2): δ 67.3
(d, 2J PP ) 34.8 Hz), 44.5 (d, 2J PP ) 34.8 Hz), -143.2 (sept, 1J PF
) 713 Hz, PF6-). 13C{1H} NMR (CD2Cl2): δ 26.9 (s, NCH2CH2),
27.9 (d, 1J PC ) 25.6 Hz, PCH2), 28.0 (d, 1J PC ) 32.7 Hz, PCH2),
40.0, 43.9 (2s, NCH2), 62.1, 63.0 (2s, OCH3), 73.1, 75.2 (2s,
CH2O), 127.4-134.5 (C6H5). FD-MS: m/z 808.7 (M+ - PF6).
Anal. Calcd for C33H44F12N2O2P4Ru: C, 41.56; H, 4.65; N, 2.94.
Found: C, 41.64; H, 4.79; N, 2.57.
24H, C6H5, C6N2H4). 31P{1H} NMR (CD2Cl2): δ 42.7 (d, 2J PP
)
2
32.6 Hz), 56.1 (d, J PP ) 32.6 Hz). 13C{1H} NMR (CD2Cl2): δ
24.5 (d, 1J PC ) 30.3 Hz, PCH2), 29.7 (d, 1J PC ) 24.3 Hz, PCH2),
53.6, 62.5 (2s, OCH3), 63.8, 74.0 (2s, CH2O), 120.3-135.3 (C6H5,
C6N2H4). FAB-MS: m/z 731.1 (M+ - BF4). Anal. Calcd for
C
39H50BClF4N2O2P2Ru: C, 54.21; H, 5.83; N, 3.24. Due to the
presence of 5d , complex 4d does not analyze well.
Com p lex 4f. Compound 3f (300 mg, 0.367 mmol) was
treated with AgBF4 (75 mg, 0.386 mmol) to give 4f: yield 281
mg (88%) of a orange powder. 1H NMR (CD2Cl2): δ 2.2-4.3
(m, 8H, CH2P, CH2O), 2.8 (s, 3H, OCH3), 2.9 (s, 3H, OCH3),
6.5-10.0 (m, 28H, C6H5, C10N2H8). 31P{1H} NMR (CD2Cl2): δ
45.9 (d, 2J PP ) 34.0 Hz), 42.9 (d, 2J PP ) 34.0 Hz). 13C{1H} NMR
Com p lex 5c. Complex 3c (300 mg, 0.408 mmol) was treated
with AgBF4 (238 mg, 1.225 mmol) to give 5c: yield 202 mg
(59%) of a yellow powder. 1H NMR (CD2Cl2): δ 0.6, 1.0, 1.1
1
1
(CD2Cl2): δ 27.7 (d, J PC ) 30.3 Hz, PCH2), 32.0 (d, J PC
)
2
3
24.3 Hz, PCH2), 58.4, 61.6 (2s, OCH3), 68.4 (d, J PC ) 5.4 Hz,
CH2O), 74.2 (s, CH2O), 123.3-159.1 (C6H5, C10N2H8). FD-MS:
m/z 781.3 (M+ - BF4). Anal. Calcd for C40H42BClF4N2O2P2Ru:
C, 55.35; H, 4.88; N, 3.23. Found:46 C, 54.68; H, 4.53; N, 2.89.
Gen er a l P r oced u r e for th e P r ep a r a tion of th e Dica t-
ion ic Com p lexes 5a -c,e-g. A solution of the neutral com-
plex 3a -c,e-g in 25 mL of dichloromethane was added to
AgBF4, AgSbF6, or TlPF6 (300% excess) and stirred for 4 h.
After filtration through silica the solvent was reduced to 5 mL
under reduced pressure. The corresponding dicationic complex
was precipitated by addition of 100 mL of diethyl ether, filtered
off (P3), and washed three times with 25 mL portions of diethyl
ether.
(3d, J HH ) 5.7, 5.6, 6.3 Hz, 9H, CHCH3), 0.7-5.0 (m, 39H,
PCH2, CH2O, H2NCH2CHNH2), 3.2, 3.3, 3.4, 3.8, 3.9, 4.0 (6s,
18H, OCH3), 6.3-7.7 (m, 60H, C6H5). 31P{1H} NMR (CD2Cl2):
2
2
isomer a (43%), δ 69.4 (d, J PP ) 35.2 Hz), 51.8 (d, J PP ) 35.2
2
2
Hz); isomer b (35%), δ 68.4 (d, J PP ) 35.4 Hz), 51.8 (d, J PP
)
2
35.4 Hz); isomer c (22%), δ 66.9 (d, J PP ) 37.3 Hz), 53.3 (d,
2J PP ) 37.3 Hz). 13C{1H} NMR (CD2Cl2): δ 17.9, 18.5, 18.6 (s,
CCH3), 28.5-31.2 (m, PCH2), 46.7, 48.3, 55.8 (s, NCH2), 49.9,
57.3, 59.7 (s, NCH), 63.8, 64.0, 65.1 (s OCH3), 67.8, 74.5, 77.3
(s, CH2O), 128.9-134.4 (C6H5). FD-MS: m/z 750.5 (M+ - BF4).
Anal. Calcd for C33H44B2F8N2O2P2Ru: C, 47.34; H, 5.30; N,
3.35. Found:46 C, 46.83; H, 5.62; N, 2.96.
Com p lex 5d . Complex 5d could not be isolated. It was
Com p lex 5a . Compound 3a (300 mg, 0.416 mmol) was
treated with AgSbF6 (429 mg, 1.249 mmol) to give 5a : yield
observed as traces in the 31P{1H} NMR spectrum of 4d .
2
31P{1H} NMR (CD2Cl2): δ 69.0 (d, J PP ) 35.8 Hz), 54.3 (d,
331 mg (71%) of a yellow powder. H NMR (CD2Cl2): δ 0.5-
2J PP ) 35.8 Hz).
1
5.2 (m, 16H, PCH2, CH2NH2, CH2O) 3.5, 4.0 (2s, 6H, OCH3),
Com p lex 5e. Compound 3e (300 mg, 0.366 mmol) was
treated with AgBF4 (213 mg, 1.099 mmol) to give 5e: yield
6.4-7.9 (m, 20H, C6H6). 31P{1H} NMR (CD2Cl2): δ 67.4 (d, 2J PP
2
1
) 35 Hz), 51.3 (d, J PP ) 35 Hz). 13C{1H} NMR (CD2Cl2): δ
216 mg (64%) of a brown powder. H NMR (CD2Cl2): δ 0.9-5
28.8 (d, 1J PC ) 31.6 Hz, PCH2), 30.9 (d, 1J PC ) 24.7 Hz, PCH2),
42.0, 48.5 (2s, NCH2), 64.2, 65.5 (2s, OCH3), 74.8, 77.7 (2s,
CH2O), 129.4-133.1 (C6H5). FD-MS: m/z 885.5 (M+ - SbF6).
(m, 12H, PCH2, CH2O, NH2), 3.7 (br, 6H, OCH3), 5.9-8.0 (m,
2
26H, C6H5, C12H6). 31P{1H} NMR (CD2Cl2): δ 57.3 (d, J PP
)
35.6 Hz), 52.2 (d, J PP ) 35.6 Hz). 13C{1H} NMR (CD2Cl2): δ
2

112 Organometallics, Vol. 21, No. 1, 2002
Nachtigal et al.
28.9 (d, 1J PC ) 27.0 Hz, PCH2), 30.0 (d, 1J PC ) 29.9 Hz, PCH2),
64.9, 66.1 (2s, OCH3), 74.2, 74.4 (2s, CH2O), 120.2-136.5 (C6H5,
(Riedel de Haen) as protecting agent. Graphite-monochro-
mated Mo KR radiation (λ ) 0.710 73 Å) was used for the
measurement of intensity data in the ω-scan mode. The data
were corrected for polarization and Lorentz effects, and an
empirical absorption correction via ψ-scans was applied for
3a . The structures were solved by direct methods with
SHELXS-86.47a Refinement was carried out with full-matrix
least-squares methods based on F2 in SHELXL-9747b with
anisotropic thermal parameters for all non-hydrogen atoms,
except the disordered toluene in 3a . Hydrogen atoms were
included at calculated positions using a riding model. Crystal
data and a summary of data collection and refinement details
are given in Table 2.
C
C
10H6). FD-MS: m/z 747.82 (M+ - 2BF4). Anal. Calcd for
40H44B2F8N2O2P2Ru: C, 52.14; H, 4.81; N, 3.04. Found:46 C,
51.52; H, 4.43; N, 3.12.
Com p lex 5f. Complex 3f (300 mg, 0.367 mmol) was treated
with AgBF4 (214 mg, 1.102 mmol) to give 5f: yield 233 mg
(69%) of a yellow powder. 1H NMR (CD2Cl2): δ 1.8-4.6 (m,
8H, PCH2, CH2O), 2.8, 3.6 (2s, 6H, OCH3), 6.4-8.5 (m, 28H,
2
C6H5, C10H8). 31P{1H} NMR (CD2Cl2): δ 57.5 (d, J PP ) 31.1
2
Hz), 40.3 (d, J PP ) 31.1 Hz). 13C{1H} NMR (CD2Cl2): δ 25.4
(d, 1J PC ) 30.6 Hz, PCH2), 28.2 (d, 1J PC ) 24.9 Hz, PCH2), 62.4,
64.7 (2s, OCH3), 75.5, 75.8 (2s, CH2O), 124.6-158.0 (C6H5,
C8H6N2). FD-MS: m/z 832.6 (M+ - BF4). Anal. Calcd for
C
40H42B2F8N2O2P2Ru: C, 52.26; H, 4.60; N, 3.05. Found:46 C,
Ack n ow led gm en t. The support of this research by
the Deutsche Forschungsgemeinschaft (Forschergruppe,
Grant FOR 184/3-1 and Graduiertenkolleg, Grant GK-
GRK 441/1-00), Bonn/Bad Godesberg, by the Fonds der
Chemischen Industrie, Frankfurt/Main, and the Wil-
helm Schuler Stiftung is gratefully acknowledged.
51.41; H, 4.27; N, 3.49.
Com p lex 5g. Complex 3g (300 mg, 0.357 mmol) was treated
with AgBF4 (208 mg, 1.071 mmol) to give 5g: yield 209 mg
1
(62%) of an auburn powder. H NMR (CD2Cl2): δ 1.6-4.6 (m,
8H, PCH2, CH2O), 2.6, 3.7 (2s, 6H, OCH3), 5.8-9.0 (m, 28H,
2
C6H5, C12H8). 31P{1H} NMR (CD2Cl2): δ 57.3 (d, J PP ) 31.6
2
Hz), 41.8 (d, J PP ) 31.6 Hz). 13C{1H} NMR (CD2Cl2): δ 25.3
(d, 1J PC ) 31.4 Hz, PCH2), 28.2 (d, 1J PC ) 24.9 Hz, PCH2), 62.4,
64.9 (2s, OCH3), 75.4, 76.2 (2s, CH2O), 126.1-158.7 (C6H5,
Su p p or tin g In for m a tion Ava ila ble: Further details of
the X-ray structure determinations, including bond distances
and angles and thermal parameters, for 3a ,e, 4b, and 5a . This
material is available free of charge via the Internet at
http://pubs.acs.org.
C
12H8N2). FD-MS: m/z 787.8 (M+ - 2BF4 + H2O). Anal. Calcd
for C42H42B2F8N2O2P2Ru: C, 53.47; H, 4.49; N, 2.97. Found:46
C, 52.71; H, 4.25; N, 3.32.
X-r a y Str u ctu r a l An a lyses for Com p lexes 3a ,e, 4b, a n d
5a . Crystals were obtained by slow diffusion of diethyl ether
into a toluene solution of 3a or dichloromethane solutions of
3e, 4b, and 5a . Selected crystals were mounted on a P4
Siemens diffractometer by using perfluorinated polyether
OM0105831
(47) (a) Sheldrick, G. M. SHELXS-86; University of Go¨ttingen,
Go¨ttingen, Germany, 1986. (b) Sheldrick, G. M. SHELXL-97; Univer-
sity of Go¨ttingen, Go¨ttingen, Germany, 1997.