A series of mononuclear ruthenium(II) complexes with sterically demanding bis(phosphino)methanes and arsino(phosphino)methanes as ligands

Article abstract of DOI:10.1016/S0022-328X(00)00339-9

The bis(η³-2-methylallyl)ruthenium(II) complexes [Ru(η³-2-MeC₃H₄)₂(κ ²-R₂PCH₂PPh₂)] (R = iPr 2, Cy 3) were prepared from the cycloocta-1.5-diene derivative [Ru(η³-2-MeC₃H₄)₂(η ⁴-C₈H₁₂)] (1) and the unsymmetrical bis(phosphino)methanes R₂PCH₂PPh₂ (R = iPr, Cy). Treatment of 2 with benzoic acid and with acetic acid in the presence of iPr₂PCH₂PPh₂ led, after proton-assisted cleavage of the allyl-metal bond, to the formation of the bis(carboxylato)ruthenium(II) compounds 4 and 5a/5b, respectively. Similarly, the bis(trifluoroacetate) [Ru(η¹-O₂CCF₃)₂(κ ²-iPr₂PCH₂PiPr₂)₂] (7) was prepared and the molecular structure determined by X-ray crystallography. The reaction of 2 and 3 with hexafluoroacetone afforded the chelate complexes [Ru(η²-acac-f₆)₂(κ²-R ₂PCH₂PPh₂)] (R = iPr 8, Cy 9) which were also accessible from [Ru(η²-OC₆Cl₅)₂(κ ²-R₂PCH₂PPh₂)] (R = iPr 10, Cy 11) by treatment with Hacac-f₆. The preparation of the non-fluorinated bis(acac) compound [Ru(η²-acac)₂(κ²-iPr ₂PCH₂PPh₂)] (12), which could not be obtained from 2 and Hacac, was achieved by ligand exchange from 10 and acetylacetone in the presence of Na₂CO₃. The reaction of 10 with CO and CNtBu gave by partial opening of the chelate rings the substitution products [Ru(OC₆Cl₅)₂(CO)(κ²-iPr ₂PCH₂PPh₂)] (13) and [Ru(OC₆Cl₅)₂(CNtBu)₃(κ ¹-Ph₂PCH₂PiPr₂)] (14), the latter containing the unsymmetrical bis(phosphino)methane as a monodentate ligand. With the dimer [RuCl(μ-Cl)(η³:η³-C₁₀H ₁₆)]₂ (15) as the starting material, the mononuclear ruthenium(IV) complexes [RuCl(η³:η³-C₁₀H ₁₆)(κ²-iPr₂PCH₂PiPr ₂)]BF₄ (16) and [RuCl₂(nη³:η³-C₁₀H ₁₆)(κ-P-iPr₂PCH₂AstBu₂)] (17) were prepared.

Full text of DOI:10.1016/S0022-328X(00)00339-9

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Journal of Organometallic Chemistry 607 (2000) 182–193
A series of mononuclear ruthenium(II) complexes with sterically
demanding bis(phosphino)methanes and
arsino(phosphino)methanes as ligands
Helmut Werner *, Guido Fries, Birgit Weberndo¨rfer
Institut fu¨r Anorganische Chemie der Uni6ersita¨t Wu¨rzburg, Am Hubland, D-97074 Wu¨rzburg, Germany
Received 17 April 2000; accepted 8 May 2000
Dedicated to Professor Martin Bennett, a good friend and creative scientist, on the occasion of his 65th birthday.
Abstract
The bis(h3-2-methylallyl)ruthenium(II) complexes [Ru(h3-2-MeC3H4)2(k2-R2PCH2PPh2)] (R=iPr 2, Cy 3) were prepared from
the cycloocta-1.5-diene derivative [Ru(h3-2-MeC3H4)2(h4-C8H12)] (1) and the unsymmetrical bis(phosphino)methanes
R2PCH2PPh2 (R=iPr, Cy). Treatment of 2 with benzoic acid and with acetic acid in the presence of iPr2PCH2PPh2 led, after
proton-assisted cleavage of the allylꢀmetal bond, to the formation of the bis(carboxylato)ruthenium(II) compounds 4 and 5a/5b,
respectively. Similarly, the bis(trifluoroacetate) [Ru(h1-O2CCF3)2(k2-iPr2PCH2PiPr2)2] (7) was prepared and the molecular
structure determined by X-ray crystallography. The reaction of 2 and 3 with hexafluoroacetone afforded the chelate complexes
[Ru(h2-acac-f6)2(k2-R2PCH2PPh2)] (R=iPr 8, Cy 9) which were also accessible from [Ru(h2-OC6Cl5)2(k2-R2PCH2PPh2)] (R=iPr
10, Cy 11) by treatment with Hacac-f6. The preparation of the non-fluorinated bis(acac) compound [Ru(h2-acac)2(k2-
iPr2PCH2PPh2)] (12), which could not be obtained from 2 and Hacac, was achieved by ligand exchange from 10 and acetylacetone
in the presence of Na2CO3. The reaction of 10 with CO and CNtBu gave by partial opening of the chelate rings the substitution
products [Ru(OC6Cl5)2(CO)(k2-iPr2PCH2PPh2)] (13) and [Ru(OC6Cl5)2(CNtBu)3(k1-Ph2PCH2PiPr2)] (14), the latter containing the
unsymmetrical bis(phosphino)methane as a monodentate ligand. With the dimer [RuCl(m-Cl)(h3:h3-C10H16)]2 (15) as the starting
material, the mononuclear ruthenium(IV) complexes [RuCl(h3:h3-C10H16)(k2-iPr2PCH2PiPr2)]BF4 (16) and [RuCl2(h3:h3-
C10H16)(k-P-iPr2PCH2AstBu2)] (17) were prepared. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Ruthenium; h3-Allyl complexes; Bis(phosphino)methane complexes; Carboxylato complexes; Pentachlorophenolato complexes
new symmetrical and unsymmetrical bis(phos-
phino)methanes and arsino(phosphino)methanes with
1. Introduction
bulky substituents R and R% at the donor centers [2,3].
The search for these ligands was initiated by the fact
that apart from the well-known compounds Ph2PCH2-
PPh2 (dppm) and Me2PCH2PMe2 (dmpm) related, in
particular unsymmetrical, derivatives of the general
composition R2PCH2PR%2 were almost unknown [4].
After we prepared at the beginning of these studies a
variety of rhodium(I) complexes with iPr2PCH2PPh2,
iPr2PCH2PCy2 [2] and iPr2PCH2AsR2 (R=iPr, tBu)
[3] as ligands, we mainly report in this paper the
synthesis of a series of ruthenium(II) compounds with
either one or two bis(phosphino)methanes linked to the
metal center. Some preliminary results of this work
have already been communicated [5].
Following our interest in the use of new, possibly
hemilabile, bidentate ligands as part of d6 and d8 metal
complexes [1], we recently described the preparation of
Scheme 1.
* Corresponding author. Tel.: +49-931-8815260; fax: +49-931-
8884605.
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00339-9

H. Werner et al. / Journal of Organometallic Chemistry 607 (2000) 182–193
183
2 and 3 are practically air-stable, readily soluble in
benzene and dichloromethane, and moderately soluble
in pentane and ether. The 31P-NMR spectra of 2 and 3
display two doublets for the non-equivalent phosphorus
nuclei with 31P–31P coupling constants of 31.7 and 30.5
Hz. In contrast to iPr2PCH2PPh2 and Cy2PCH2PPh2,
the starting material
1
does not react with
iPr2PCH2AstBu2 and is recovered unchanged after
heating the reaction mixture in hexane for 6 h under
reflux.
The molecular structure of compound 2, of which
single crystals were obtained from ether at 0°C, was
determined by X-ray crystallography. The ORTEP plot
(Fig. 1) reveals that the coordination geometry can be
regarded as pseudo-tetrahedral with the two phospho-
rus atoms P1 and P2 and the two central carbon atoms
C3 and C7 of the allylic units at the corners of the
tetrahedron. The bond lengths RuꢀC3 and RuꢀC7 are
significantly shorter than those from ruthenium to the
terminal carbon atoms of the 2-MeC3H4 ligands. This
results in dihedral angles of 40.66(24) and 39.08(38)°
between the planes of the p-allylic systems, [C2,C3,C4]
and [C6,C7,C8], and the plane of the four-membered
chelate ring [Ru,P1,C1,P2]. The carbon atoms C3 and
C7 are bent away from the metal center, analogously as
found in [Ru(h3-C3H5)2(PPh3)2] [8]. The distances
RuꢀP1 and RuꢀP2 differ only slightly to those in other
phosphineruthenium(II) complexes [8,9] while the bite
angle P1ꢀRuꢀP2 of 72.06(7)° is almost the same as in
some compounds with Ru(dppm) as the molecular unit
[10].
Fig. 1. Molecular structure (ORTEP diagram) of compound 2. Selected
,
bond lengths (A) and bond angles (°): RuꢀP1 2.286(2), RuꢀP2
2.345(2), RuꢀC2 2.237(2), RuꢀC3 2.185(2), RuꢀC4 2.238(2), RuꢀC6
2.227(2), RuꢀC7 2.172(2), RuꢀC8 2.232(2), P1ꢀC1 1.842(4), P2ꢀC1
1.848(4); P1ꢀRuꢀP2 72.06(7), RuꢀP1ꢀC1 97.5(1), RuꢀP2ꢀC1 95.3(1),
P1ꢀC1ꢀP2 95.2(2), C2ꢀC3ꢀC4 117.5(4), C6ꢀC7ꢀC8 118.7(4).
2. Results and discussion
Applying the methodology, recently developed by
Holle et al. [6] and Leitner and coworkers [7], we
prepared the bis(h3-2-methylallyl)ruthenium(II) com-
plexes 2 and 3 (Scheme 1) from the cycloocta-1.5-diene
derivative 1 as the starting material. The reaction pro-
ceeds in hexane under reflux conditions and gives the
products as yellow solids in 75–82% yield. Compounds
Likewise to the cycloocta-1.5-diene complex 1, which
upon treatment with CF3CO2H affords the dinu-
clear product [Ru(m-O2CCF3)2(h4-C8H12)]2 [11], the
analogous compound 2 is also quite reactive towards
Scheme 2.

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H. Werner et al. / Journal of Organometallic Chemistry 607 (2000) 182–193
Fig. 2. Comparision of the measured (a) and the simulated (b) 31P-NMR spectrum (AA%BB% spin system) of compound 5a.
Treatment of the bis(h3-2-methylallyl)ruthenium(II)
carboxylic acids. With benzoic acid, the mononuclear
complex 4 (Scheme 2) is formed in which both benzoate
anions are coordinated as bidentate ligands to the metal
center. The IR spectrum of 4 displays two w(OCO)
bands at 1493 and 1415 cm−1, the positions of which
are typical for a chelating bonding mode of the PhCO2−
units [12].
compound 6, containing the symmetrical chelating lig-
and iPr2PCH2PiPr2, with CF3CO2H in the presence of
an equimolar amount of bis(diisopropylphos-
phino)methane, leads to the formation of the octahe-
dral complex 7. An alternative preparative pathway to
compound 7, which is structurally related to the iso-
meric bis(acetato) derivatives 5a/5b, consists in the re-
action of 1 with two equivalents of both CF3CO2H and
iPr2PCH2PiPr2 (Scheme 3). In either way, the isolated
yield of 7 is about 80%. The 31P-NMR spectrum of 7
displays one singlet resonance at l −2.3, while the IR
spectrum shows two bands at 1683 and 1456 cm−1 for
the symmetrical and antisymmetrical w(OCO) stretching
frequencies.
The reactions of 2 with CH3CO2H and CF3CO2H
led, either at −78°C or at room temperature, to a
mixture of products which could not be separated by
fractional crystallization or chromatographic tech-
niques. If, however, the bis(h3-2-methylallyl) compound
2 is treated with acetic acid in ether in the presence of
an equimolar amount of iPr2PCH2PPh2, a yellow, only
slightly air-sensitive solid can be isolated in 72% yield.
The 31P-NMR spectrum of the product indicates that
two stereoisomers, 5a and 5b, in the ratio of approxi-
mately 85:15 are formed. For the major isomer 5a, in
which the two PPh2 and the two PiPr2 units are cis to
each other, four signals appear which are part of an
AA%BB% spin system. From the simulation (see Fig. 2),
The result of the X-ray crystal structure analysis of 7
is illustrated in Fig. 3. The coordination sphere around
the metal center corresponds to a perfect octahedron
with PꢀRuꢀP and OꢀRuꢀO bond angles of 180°. The
trifluoroacetate ligands are trans disposed, the planes
four 31P–31P coupling constants of 301.6 (JP1,P3
=
JP2,P4), −37.0 (JP1,P4=JP2,P3), −23.6 and −23.3 Hz
have been determined, of which the last two represent
either a P1,P2 or a P3,P4 coupling. These values are in
good agreement with data reported by Baker and Field
for the six-coordinate ruthenium(II) complex trans-
[RuCl2(PMe2Ph)2(k2-Ph2PCH2PPh2)] [13]. The minor,
centro-symmetrical isomer 5b shows two doublets of
doublets with 31P–31P coupling constants of 30.3 and
28.6 Hz, respectively. The IR spectrum of 5a/5b, in
which two OCO stretching frequencies at 1583 and
1389 cm−1 appear, supports the assumption that the
two acetate ligands are linked in a monodentate fashion
to the metal center.
Scheme 3.

H. Werner et al. / Journal of Organometallic Chemistry 607 (2000) 182–193
185
[Ru(h2-O2CCH3)(k2-Ph2PCH2PPh2)2]+ [10c] where in-
stead of PiPr2 two less bulky PPh2 groups are present.
The 2-methylallyl ligands in compounds 2 and 3 can
also be substituted by the anion of hexafluoroacetylace-
tone. Treatment of 2 or 3 with Hacac-f6 in benzene or
toluene yields the chelate complexes 8 and 9 (Scheme 4)
as red air-stable solids in almost quantitative yield. Due
to the coordination of the unsymmetrical bis(phos-
phino)methane, the two acac-f6 units are non-equiva-
lent and therefore both the 13C- and 19F-NMR spectra
of 8 and 9 display four resonances for the carbon and
fluor nuclei of the CF3 groups in the rather narrow
ranges of l 118.4 to 117.1 (13C) and −75.7 to −74.4
(19F), respectively.
In contrast to Hacac-f6, the non-fluorinated counter-
part Hacac does not react, even in refluxing toluene,
with either 2 or 3. We assume that the lower acidity of
acetylacetone (pKs=9.0) compared to the hexafluoro
analogue (pKs=5.3) [15] explains the difference in the
reactivity of the two diketones toward the bis(h3-2-
methylallyl)ruthenium(II) complexes.
However, the wanted bis(acac) derivative 12 can be
prepared indirectly via the bis(pentachloropheno-
lato)metal compound 10 as an intermediate. Both 10
and 11 are obtained upon treatment of 2 or 3 with
C6Cl5OH in toluene at room temperature as yellow
solids in 98 and 95% yield. With regard to the spectro-
scopic data of 10 and 11, the interesting feature is that
in the 13C-NMR spectra at 300 K instead of ten only
Fig. 3. Molecular structure (ORTEP diagram) of compound 7. Selected
,
bond lengths (A) and bond angles (°): RuꢀP1 2.3938(8), RuꢀO1
2.121(3), O1ꢀC2 1.260(6), O2ꢀC2 1.213(6); P1ꢀRuꢀP1C 71.14(4),
P1ꢀRuꢀP1B 108.86(4), P1ꢀRuꢀP1A 180.0, O1ꢀRuꢀO1A 180.0.
containing the atoms O1,C2,O2 and O1A,C2A,O2A are
perpendicular to the basal plane with the metal and the
phosphorus atoms. The four RuꢀP distances of
,
2.3938(8)
A
are similar to those in [Ru(h1-
O2CCF3)2(BIPHOS)2] [14] and in the cationic complex
Scheme 4.

186
H. Werner et al. / Journal of Organometallic Chemistry 607 (2000) 182–193
Scheme 5.
cm−1 and the 13C-NMR spectrum only one resonance
in the typical region for MꢀCO carbon atoms, there is
no doubt that a monocarbonyl compound is obtained.
The 31P-NMR spectrum of 13 shows at room tempera-
ture two broad signals at l 28.5 and 6.5, which upon
cooling to 245 K split into two sharp doublets at l 28.5
and 13.9 and two rather broad doublets at l 43.2 and
9.2, respectively. Further lowering of the temperature
to 217 K results in a sharpening of the latter two signals
which now appear as sharp doublets with a 31P–31P
coupling constant of 68.7 Hz. At 325 K, the 31P-NMR
spectrum of 13 is quite simple and shows two doublets
at l 35.4 and 11.6 with J(PP)=71.3 Hz. We assume
that the strong temperature-dependence of the 31P-
NMR spectrum of 13 is due to a dynamic process
which at room temperature and above involves a fast
cleavage and reformation of one RuꢀCl bond. Under
these conditions, there is probably an equilibrium be-
tween the five-coordinate species, depicted in Scheme 5,
and two six-coordinate isomers (with one h1- and one
h2-OC6Cl5 units), in one of which the CO ligand is
trans to the PiPr2 and in the other trans to the PPh2
moiety. At 217 K, this process is extremely slow (on the
NMR time scale) and thus the two frozen isomers can
be observed. A similar situation exists in the case of the
corresponding monocarbonylruthenium(II) complex
[RuCl2(CO)(k-P-iPr2PCH2CO2Me)(k2-P,O-iPr2PCH2-
CO2Me)] where at elevated temperatures an exchange
between the monodentate and the bidentate phosphi-
nocarboxylate ligands occurs [1g].
six signals for the 13C nuclei of the CꢀCl moieties
appear. The most reasonable explanation for this obser-
vation is that under these conditions the two complexes
exhibit a fluxional behavior which involves (on the
NMR time scale) a rapid coordination–decoordination
of the ortho-chlorine atoms of the six-membered rings
to the metal center and thus leads to an equivalence of
the carbons atoms in ortho and meta positions of each
of the two OC6Cl5 units. The 13C-NMR spectrum of 10
displays at 188 K, apart from the two signals for the
ipso-C atoms, the expected ten resonances for the ortho,
meta and para carbon atoms of the C6Cl5 rings, indicat-
ing that at this temperature a rigid structure for the
molecule can be assumed. It seems that the stability of
the chelating bonding mode (via oxygen and chlorine)
of pentachlorophenolate ligands to ruthenium depends
considerably on the coordination sphere since the hy-
drido compound [RuH(h2-OC6Cl5)(CO)(PiPr3)2] is non-
fluxional on the NMR time scale at room temperature
[16] while the complex [Ru(h2-OC6Cl5)2(k2-iPr2PCH2-
CH2PPh2)] reveals a dynamic behavior resulting in an
equivalence of the ortho-disposed CꢀCl units even at
188 K [17].
Due to the lability of the RuꢀOC6Cl5 linkages, com-
pound 10 does not only react quite smoothly with
Hacac-f6 to give 8 but also, in the presence of Na2CO3,
with acetylacetone to afford the bis(acac) complex 12
(see Scheme 4). The isolated yield of 12 was 96%.
Without Na2CO3, no reaction occurs. The bidentate
coordination mode of the acac ligands in 12 is indicated
by the appearance of two strong IR bands at 1575 and
1512 cm−1, that is in a very similar position as in
various other M(h2-acac) derivatives [18].
In contrast to CO, the starting material 10 reacts
with CNtBu to give the tris(isocyanide)ruthenium(II)
compound 14 in 87% yield. The unexpected addition of
three isocyanide ligands to the metal center is not only
supported by the elemental analysis but even more by
the appearance of two signals for the CNCCH3 protons
A partial cleavage of the Ru(h2-OC6Cl5) chelates
takes place upon treatment of 10 with carbon monoxide
and tert-butylisocyanide (Scheme 5). Passing a stream
of CO through a solution of 10 in benzene leads to a
change of color from orange–red to yellow and after
removal of the solvent affords the slightly air-sensitive
complex 13 in 85% isolated yield. Since the IR spectrum
of 13 displays only one intense w(CO) band at 1971
1
in the H-NMR spectrum at l 1.21 and 1.01 in the
relative ratio of 2:1 (or 18:9, respectively). The 13C-
NMR spectrum of 14 leaves no doubt that the two
OC6Cl5 units are identical. Although on the basis of the
spectroscopic data it can not conclusively be decided

H. Werner et al. / Journal of Organometallic Chemistry 607 (2000) 182–193
187
forms a chelate bond with the [RuCl(h3:h3-C10H16)]+
fragment thus generating a cationic ruthenium(IV)
complex with the coordination number seven at the
metal center.
whether the PiPr2 or the PPh2 fragment of the bis(phos-
phino)methane ligand is linked to ruthenium, the
smooth reaction of 14 with oxygen indicates that the
more bulky PiPr2 moiety is not involved in coordina-
tion. After leaving the solution of 14 (in C6D6) in air, in
the 31P-NMR spectrum instead of the signal at l 3.6
(J(PP)=69.1 Hz) a new doublet resonance at l 40.9
(J(PP)=11.1 Hz) is observed which we tentatively
assign to a P(O)iPr2 unit. It should be mentioned that
both the 1H- and 13C-NMR spectra of 14 are not
temperature-dependent which means that in solution no
dynamic process takes place.
For comparison, we have not only studied the reac-
tivity of the bis(h3-allyl) complex 1 but also that of the
chain-like octadienediyl compound 15 toward
iPr2PCH2PPh2. In the presence of AgBF4, a clean reac-
tion occurs which, after separation of AgCl and evapo-
ration of the solvent, affords the ionic complex 16
(Scheme 6) in 82% yield. Apart from the elemental
analysis, the conductivity measurement confirms that a
1:1 electrolyte has been formed. The 31P-NMR spec-
trum of 16 displays two doublet resonances at l −14.2
and −20.0 with a 31P–31P coupling of 48.3 Hz.
The reaction of 15 with the sterically demanding
arsino(phosphino)methane iPr2PCH2AstBu2 results in
the cleavage of the chlorine bridges and the formation
of the mononuclear complex 17. The 31P-NMR spec-
trum of the orange, practically air-stable species dis-
plays a singlet at l 25.0, the position of which indicates
that the PiPr2 unit is coordinated to ruthenium. At-
tempts to generate a cationic complex, structurally re-
lated to 16, by treatment of 17 with NaBPh4 failed.
In summary, we have shown that the new unsymmet-
rical bis(phosphino)methanes R2PCH2PPh2, containing
two bulky substituents such as cyclohexyl or isopropyl
at one of the donor centers, prefer to coordinate to
ruthenium(II) in a chelating fashion. The anionic lig-
ands which complete the coordination sphere could be
either h3-allyl, carboxylates, fluorinated or unfluori-
nated acetylacetonates, and — quite remarkably —
also pentachlorophenolate. The symmetrical bis-
(phosphino)methane derivative iPr2PCH2PiPr2 even
3. Experimental
All experiments were carried out under an atmo-
sphere of argon by using Schlenk techniques. The start-
ing materials 1 [19], 6 [6], 15 [20] as well as the ligands
iPr2PCH2PiPr2, R2PCH2PPh2 (R=iPr, Cy) [2] and
iPr2PCH2AstBu2 [2] were prepared according to pub-
lished methods. IR: Perkin–Elmer 1320. NMR: Bruker
AC 200 and AMX 400. Mass spectra: Finnigan 90
MAT and 8200 MAT. Melting and decomposition
points were determined by DTA.
3.1. Preparation of
[Ru(p3-2-MeC3H4)2(s2-iPr2PCH2PPh2)] (2)
A suspension of 228 mg (0.71 mmol) of 1 in 10 ml of
hexane was treated with a solution of 226 mg (0.71
mmol) of iPr2PCH2PPh2 in 10 ml of hexane and heated
under reflux for 12 h. After cooling to r.t., the solvent
was evaporated in vacuo, the remaining yellow solid
was washed with 10 ml of pentane and dried. Yield 281
mg (75%), m.p. 147°C. Anal. Found: C, 61.02; H, 7.70.
1
Calc. for C27H40P2Ru: C, 61.46; H, 7.64%. H-NMR
(400 MHz, CD2Cl2): l 7.90 (m, 2H, C6H5), 7.40, 7.22
(both m, 3H each, C6H5), 7.01 (m, 2H, C6H5), 4.15 (m,
1H, one H of P1CH2P2), 3.83 [ddd, J(P1H)=14.8,
J(P2H)=9.6, J(HH)=7.6 Hz, 1H, one H of P1CH2P2),
2.60 (m, 2H, C3H4), 2.29, 2.02 (both m, 1H each,
PCHCH3), 1.92, 1.79 (both s, 3H each, C3H4CH3), 1.70
(d, J(PH)=12.4 Hz, 1H, one H of C3H4), 1.58 (dd,
J(P1H)=13.8, J(P2H)=5.0 Hz, 1H, one H of C3H4),
1.42 (dd, J(PH)=15.2, J(HH)=7.6 Hz, 3H,
PCHCH3), 1.32 (dd, J(PH)=13.2, J(HH)=7.2 Hz,
3H, PCHCH3), 1.08 (dd, J(PH)=J(HH)=2.4 Hz, 1H,
one H of C3H4), 1.02 (m, 1H, one H of C3H4), 1.00 (dd,
J(PH)=10.8, J(HH)=7.2 Hz, 3H, PCHCH3), 0.86
Scheme 6.

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H. Werner et al. / Journal of Organometallic Chemistry 607 (2000) 182–193
(dd, J(PH)=13.4, J(HH)=7.6 Hz, 3H, PCHCH3),
0.53 (dd, J(P1H)=15.2, J(P2H)=4.8 Hz, 1H, one H of
C3H4), 0.48 (d, J(PH)=14.4 Hz, 1H, one H of C3H4).
13C-NMR (100.6 MHz, CD2Cl2): l 140.8 (dd, J(P1C)=
30.0, J(P2C)=3.5 Hz, ipso-C of C6H5), 135.3 (dd,
J(P1C)=14.1, J(P2C)=11.1 Hz, ipso-C of C6H5),
133.6 (d, J(PC)=14.1, ortho-C of C6H5), 131.2 (d,
J(PC)=8.0 Hz, ortho-C of C6H5), 129.4 (d, J(PC)=
2.0 Hz, para-C of C6H5), 128.2 (d, J(PC)=7.1 Hz,
meta-C of C6H5), 128.1 (d, J(PC)=2.0 Hz, para-C of
C6H5), 128.0 (d, J(PC)=9.0 Hz, meta-C of C6H5),
95.5, 94.9 (both s, CCH3 of C4H7), 41.8, 41.6 (both d,
J(PC)=15.3 Hz, CH2 of C4H7), 38.8, 38.6 (both d,
J(PC)=3.8 Hz, CH2 of C4H7), 35.5 (dd, J(P1C)=16.1,
J(P2C)=3.3 Hz, P1CH2P2), 32.4 (d, J(PC)=18.2 Hz,
PCHCH3), 27.3 (d, J(PC)=7.5 Hz, PCHCH3), 25.8,
25.6 (both s, CCH3 of C4H7), 20.4 (d, J(PC)=5.6 Hz,
PCHCH3), 20.0 (s, PCHCH3), 19.7 (d, J(PC)=2.1 Hz,
PCHCH3), 19.4 (d, J(PC)=2.9 Hz, PCHCH3). 31P-
NMR (162.0 MHz, CD2Cl2): l 14.4 (d, J(PP)=31.7
Hz, PiPr2), 12.7 (d, J(PP)=31.7 Hz, PPh2).
3.3. Preparation of
[Ru(p2-O2CPh)2(s2-iPr2PCH2PPh2)] (4)
A solution of 83 mg (0.16 mmol) of 2 in 10 ml of
ether was treated at −78°C with a solution of 39 mg
(0.32 mmol) of benzoic acid in 5 ml of ether. After
warming to r.t., the solvent was evaporated in vacuo,
the remaining yellow solid was washed twice with 5 ml
of pentane and dried. Yield 62 mg (60%). IR (C6H6):
w(OCOasym) 1493, w(OCOsym) 1415 cm−1 1H-NMR
.
(400 MHz, C6D6): l 8.39–6.81 (m, 20H, C6H5), 4.30,
3.78 (both m, 1H each, P1CH2P2), 2.28 (m, 2H,
PCHCH3), 1.44 (dd, J(PH)=15.7, J(HH)=7.2 Hz,
3H, PCHCH3), 1.23 (dd, J(PH)=15.8, J(HH)=7.0
Hz, 3H, PCHCH3), 1.19 (dd, J(PH)=14.7, J(HH)=
7.0 Hz, 3H, PCHCH3), 1.11 (dd, J(PH)=13.4,
J(HH)=7.2 Hz, 3H, PCHCH3). 13C-NMR (100.6
MHz, C6D6): l 180.6, 178.0 (both s, OCO), 137.2 (d,
J(PC)=2.8 Hz, C6H5), 136.7 (d, J(PC)=4.6 Hz,
C6H5), 136.4 (d, J(PC)=3.8 Hz, C6H5), 136.1 (s,
C6H5), 135.7 (d, J(PC)=36.2 Hz, ipso-C of C6H5),
133.5, 132.1 (both d, J(PC)=10.5 Hz, C6H5), 130.4 (s,
C6H5), 130.0 (d, J(PC)=6.7 Hz, C6H5), 129.9 (d,
J(PC)=9.5 Hz, C6H5), 129.4, 128.9, (both s, C6H5),
128.7 (d, J(PC)=10.5 Hz, C6H5), 128.2 (d, J(PC)=
23.8 Hz, ipso-C of C6H5), 127.8 (d, J(PC)=13.4 Hz,
C6H5), 42.7 (dd, J(P1C)=21.0, J(P2C)=14.3 Hz,
P1CH2P2), 26.4 (d, J(PC)=19.0 Hz, PCHCH3), 24.9 (s,
PCHCH3), 20.1, 19.7 (both s, PCHCH3), 19.2, 18.1
(both d, J(PC)=2.7 Hz, PCHCH3). 31P-NMR (162.0
MHz, C6D6): l 36.3 (d, J(PP)=89.1 Hz, PiPr2), 20.8
(d, J(PP)=89.1 Hz, PPh2).
3.2. Preparation of
[Ru(p3-2-MeC3H4)2(s2-Cy2PCH2PPh2)] (3)
This was carried out analogously as described for 2,
using 112 mg (0.35 mmol) of 1 and 128 mg (0.35 mmol)
of Cy2PCH2PPh2 as starting materials; time for reflux
was 4 h. Yellow solid; yield 174 mg (82%), m.p. 101°C.
Anal. Found: C, 65.43; H, 7.56. Calc. for C33H48P2Ru:
1
C, 65.22; H, 7.96%. H-NMR (400 MHz, C6D6): l 8.08
(m, 2H, C6H5), 7.27–6.94 (m, 8H, C6H5), 4.04, 3.66
(both m, 1H each, P1CH2P2), 3.22, 3.01, 2.54 (all br m,
1H each, CH2 of C3H4), 2.35, 2.19 (both s, 3H each,
C3H4CH3), 2.19–0.90 (m, 27H, CH2 of C3H4 and
C6H11). 13C-NMR (100.6 MHz, C6D6): l 135.6 (dd,
J(P1C)=14.2, J(P2C)=9.1 Hz, ipso-C of C6H5), 133.8
(d, J(PC)=14.2 Hz, ortho-C of C6H5), 131.2 (d,
J(PC)=8.1 Hz, ortho-C of C6H5), 129.3 (d, J(PC)=
2.0 Hz, para-C of C6H5), 128.3 (d, J(PC)=7.6 Hz,
meta-C of C6H5), 128.0 (d, J(PC)=1.7 Hz, para-C of
C6H5), 127.9 (d, J(PC)=9.5 Hz, meta-C of C6H5),
95.7, 95.6 (both s, CCH3 of C4H7), 44.0 (dd, J(P1C)=
10.2, J(P2C)=6.1 Hz, CH of C6H11), 40.0 (dd,
J(P1C)=17.5, J(P2C)=14.2 Hz, P1CH2P2), 39.1 (d,
J(PC)=3.0 Hz, CH2 of C4H7), 38.9 (d, J(PC)=4.1 Hz,
CH2 of C4H7), 38.2 (d, J(PC)=5.1 Hz, CH of C6H11),
36.2, 36.0 (both d, J(PC)=4.1 Hz, CH2 of C4H7), 30.7
(s, CH2 of C6H11), 30.6 (d, J(PC)=4.1 Hz, CH2 of
C6H11), 30.2 (s, CH2 of C6H11), 29.5 (d, J(PC)=3.1 Hz,
CH2 of C6H11), 28.2 (d, J(PC)=12.2 Hz, CH2 of
C6H11), 27.8 (d, J(PC)=9.2 Hz, CH2 of C6H11), 27.6
(d, J(PC)=7.1 Hz, CH2 of C6H11), 27.3 (d, J(PC)=
10.2 Hz, CH2 of C6H11), 26.8, 26.5 (both s, CH2 of
C6H11), 26.8, 26.1 (both s, CCH3 of C4H7). 31P-NMR
(162.0 MHz, C6D6): l 14.7 (d, J(PP)=30.5 Hz, Cy2P),
6.0 (d, J(PP)=30.5 Hz, Ph2P).
3.4. Preparation of
[Ru(p1-O2CCH3)2(s2-iPr2PCH2PPh2)2] (5a,b)
A solution of 148 mg (0.28 mmol) of 2 and 89 mg
(0.28 mmol) of iPr2PCH2PPh2 in 5 ml of ether was
treated at −78°C with 32 ml (0.56 mmol) of acetic acid.
After warming to r.t., the solution was stirred for 10
min which led to a change of color from yellow to
orange. The solvent was evaporated in vacuo, the re-
maining yellow solid was washed twice with 5 ml of
pentane and dried. Yield 172 mg (72%), m.p. 152°C.
Anal. Found: C, 58.77; H, 7.24. Calc. for
C42H58O4P4Ru: C, 59.22; H, 6.86%. IR (CH2Cl2):
w(OCOasym) 1583, w(OCOsym) 1389 cm−1 1H-NMR
.
(400 MHz, CD2Cl2): l 7.20–7.00 (m, 20H, C6H5), 4.99
(m, 4H, P1CH2P2), 2.70 (m, 4H, PCHCH3), 1.36–1.10
(m, 24H, PCHCH3). 13C-NMR (100.6 MHz, CD2Cl2): l
179.2, 178.5 (both s, OC(O)CH3), 137.0, 132.5, 128.2
(all br m, C6H5), 46.0 (br m, P1CH2P2), 26.3 (d,
J(PC)=7.8 Hz, PCHCH3), 24.7 (s, OC(O)CH3), 19.5–
18.4 (br m, PCHCH3). 31P-NMR (162.0 MHz,
CD2Cl2): l 6.0 (dd, J(PP)=30.3, J(PP%)=28.6 Hz,
PiPr2), 1.9–4.5 (br m), −5.3 (dd, J(PP)=30.3 Hz,
J(PP%)=28.6 Hz, PPh2).

H. Werner et al. / Journal of Organometallic Chemistry 607 (2000) 182–193
189
3.5. Preparation of
C6H5), 131.6 (d, J(PC)=40.7 Hz, ipso-C of C6H5),
131.1 (d, J(PC)=1.9 Hz, C6H5), 130.5 (d, J(PC)=11.1
Hz, C6H5), 130.1, 128.8 (both d, J(PC)=2.8 Hz,
C6H5), 128.6 (d, J(PC)=3.7 Hz, C6H5), 118.4, 118.2
(both q, J(FC)=284.8 Hz, CF3), 117.2, 117.1 (both q,
J(FC)=283.8 Hz, CF3), 91.5, 90.8 (both s, CH of
acac-f6), 42.2 (dd, J(P1C)=23.1, J(P2C)=17.6 Hz,
P1CH2P2), 25.4 (dd, J(P1C)=17.1, J(P2C)=3.7 Hz,
PCHCH3), 24.1 (d, J(PC)=19.4 Hz, PCHCH3), 18.6
(d, J(PC)=2.7 Hz, PCHCH3), 18.3 (d, J(PC)=1.9 Hz,
PCHCH3), 18.0 (s, PCHCH3), 17.5 (d, J(PC)=1.8 Hz,
PCHCH3). 19F-NMR (188.3 MHz, C6D6): l −75.7,
−75.5, −74.7, −74.6, (all s). 31P-NMR (81.0 MHz,
C6D6): l 34.5 (d, J(PP)=80.1 Hz, PiPr2), 15.2 (d,
J(PP)=80.1 Hz, PPh2).
[Ru(p1-O2CCF3)2(s2-iPr2PCH2PiPr2)2] (7)
(a) A solution of 102 mg (0.35 mmol) of 1 and 174
mg (0.70 mmol) of iPr2PCH2PiPr2 in 6 ml of ether was
treated with 54 ml (0.70 mmol) of CF3CO2H at r.t.
After the solution was heated under reflux for 6 h, it
was cooled to r.t. and the solvent was evaporated in
vacuo. The remaining yellow microcrystalline solid was
washed with 3 ml of pentane and dried; yield 224 mg
(78%).
(b) A solution of 138 mg (0.30 mmol) of 6 and 75 mg
(0.30 mmol) of iPr2PCH2PiPr2 in 5 ml of ether was
treated at −78°C with 48 ml (0.60 mmol) of CF3CO2H.
After the solution was warmed to r.t., it was stirred for
10 min and then worked up as described for a); yield
203 mg (82%), m.p. 145°C. Anal. Found: C, 43.41; H,
7.02. Calc. for C30H60F6O4P4Ru: C, 43.74; H, 7.34%.
3.7. Preparation of [Ru(p2-acac-f6)2(s2-Cy2PCH2PPh2)]
(9)
IR (CH2Cl2): w(OCOasym) 1683, w(OCOsym) 1456 cm−1
.
1H-NMR (400 MHz, CD2Cl2): l 4.43 (m, 4H, PCH2P),
2.34 (s, 8H, PCHCH3), 1.39–1.15 (m, 48H, PCHCH3).
13C-NMR (100.6 MHz, CD2Cl2): l 164.9 (br m, CO2),
113.5 (q, J(FC)=292.7 Hz, CF3), 40.5 (m, PCH2P),
27.4 (d, J(PC)=4.4 Hz, PCHCH3), 19.7, 18.3 (both s,
PCHCH3).19F-NMR (376.5 MHz, CD2Cl2): l −75.5
(s). 31P-NMR (162.0 MHz, CD2Cl2): l −2.3 (s).
A solution of 259 mg (0.43 mmol) of 3 in 5 ml of
toluene was treated dropwise at −78°C with 122 ml
(0.87 mmol) of hexafluoroacetylacetone.
A rapid
change of color from yellow to dark red occurred. After
the reaction mixture was warmed to r.t., it was stirred
for 10 min, and than the solvent was evaporated in
vacuo. The residue was dissolved in 2 ml of ether and
the solution was chromatographed on Al2O3 (basic,
activity grade I, height of column 12 cm). With 1:1
ether–pentane a dark red fraction was eluted which
after removal of the solvent gave a dark red solid. Yield
327 mg (97%), m.p. 142°C. Anal. Found: C, 52.34; H
4.48. Calc. for C35H36F12O4P2Ru: C, 52.70; H, 4.55%.
3.6. Preparation of
[Ru(p2-acac-f6)2(s2-iPr2PCH2PPh2)] (8)
(a) A solution of 132 mg (0.25 mmol) of 2 in 8 ml of
benzene was treated dropwise with 71 ml (0.50 mmol) of
hexafluoroacetylacetone, which led to a rapid change of
color from yellow to dark red. After stirring for 20 min,
the solvent was evaporated in vacuo and the residue
was dissolved in 5 ml of pentane. The solution was
filtered and the filtrate was brought to dryness in vacuo
to give a dark red solid; yield 201 mg (97%).
IR (CH2Cl2): w(acac-f6) 1623, 1501 cm−1 1H-NMR
.
(400 MHz, CDCl3): l 7.65 (m, 2H, C6H5), 7.42–7.06
(br m, 8H, C6H5), 6.07, 5.71 (both s, 1H each, CH of
acac-f6), 4.18–3.95 (br m, 2H, P1CH2P2), 2.09–0.85 (br
m, 22H, C6H11). 13C-NMR (100.6 MHz, CDCl3): l
174.8, 174.2, 171.9, 171.8 (all q, J(FC)=34 Hz, CO of
acac-f6), 133.2 (dd, J(P1C)=38.1, J(P2C)=13.5 Hz,
ipso-C of C6H5), 132.8 (d, J(PC)=11.2 Hz, ortho-C of
C6H5), 131.6 (d, J(PC)=38.7 Hz, ipso-C of C6H5),
130.6 (d, J(PC)=3.0 Hz, para-C of C6H5), 130.4 (d,
J(PC)=11.2 Hz, ortho-C of C6H5), 129.8 (d, J(PC)=
2.0 Hz, para-C of C6H5), 128.5, 128.4 (both d, J(PC)=
10.2 Hz, meta-C of C6H5), 117.7, 117.6, 117.5, 117.4
(all q, J(FC)=284.5 Hz, CF3), 90.9, 90.3 (both s, CH
of acac-f6), 40.3 (dd, J(P1C)=22.9, J(P2C)=17.8 Hz,
P1CH2P2), 35.6 (dd, J(P1C)=16.8, J(P2C)=2.5 Hz,
CH of C6H11), 35.1 (d, J(PC)=17.3 Hz, CH of C6H11),
28.8, 28.5, 28.4, 27.2, 26.0, 25.6 (all s, CH2 of C6H11),
28.3, 27.4, 26.8, 26.7 (all d, J(PC)=3.1 Hz, CH2
of C6H11), 19F-NMR (376.5 MHz, CDCl3): l −75.7,
−75.5, −74.6, −74.4, (all s). 31P-NMR (162.0 MHz,
CDCl3): l 25.2 (d, J(PP)=76.3 Hz, Cy2P), 15.9 (d,
J(PP)=76.3 Hz, Ph2P).
(b) A solution of 125 mg (0.13 mmol) of 10 in 5 ml
of toluene was treated with 37 ml (0.26 mmol) of
hexafluoroacetylacetone. After stirring for 5 min at r.t.,
the solution was worked up as described for a). Yield
99 mg (92%), m.p. 91°C. Anal. Found: C, 42.34; H,
3.24. Calc. for C29H28F12O4P2Ru: C, 41.89; H, 3.39%.
IR (CH2Cl2): w(acac-f6) 1733, 1608 cm−1 1H-NMR
.
(200 MHz, C6D6): l 7.74 (m, 2H, C6H5), 7.02 (m, 8H,
C6H5), 6.45, 6.06 (both s, 1H each, CH of acac-f6),
3.82–3.49 (br m, 2H, P1CH2P2), 2.22, 1.64 (both br m,
1H each, PCHCH3), 1.17 (dd, J(PH)=16.4, J(HH)=
7.3 Hz, 3H, PCHCH3), 0.99 (dd, J(PH)=14.6,
J(HH)=7.3 Hz, 3H, PCHCH3), 0.64 (dd, J(PH)=
15.8, J(HH)=6.9 Hz, 3H, PCHCH3), 0.54 (dd,
J(PH)=16.1, J(HH)=6.9 Hz, 3H, PCHCH3). 13C-
NMR (50.3 MHz, C6D6): l 175.5, 174.8, 172.7, 172.6
(all q, J(FC)=34 Hz, CO of acac-f6), 133.9 (d,
J(PC)=3.7 Hz, C6H5), 133.0 (d, J(PC)=11.1 Hz,

190
H. Werner et al. / Journal of Organometallic Chemistry 607 (2000) 182–193
3.8. Preparation of
10H, C6H5), 3.25–0.43 (br m, 24H, P1CH2P2 and
C6H11). 13C-NMR (100.6 MHz, C6D6): l 162.8, 162.6
(both s, ipso-C of C6Cl5), 134.2 (dd, J(P1C)=12.2,
J(P2C)=7.0 Hz, ipso-C of C6H5), 133.9 (d, J(PC)=
14.2 Hz, C6H5), 131.4 (d, J(PC)=8.0 Hz, C6H5), 129.9,
128.1 (both d, J(PC)=1.9 Hz, C6H5), 128.6 (d,
J(PC)=7.3 Hz, C6H5), 127.6 (d, J(PC)=7.5 Hz,
C6H5), 125.7, 125.4, 118.6, 118.0, 116.9, 116.2 (all s,
C6Cl5), 43.9 (dd, J(P1C)=12.2, J(P2C)=6.0 Hz, CH of
C6H11), 40.2 (dd, J(P1C)=17.8, J(P2C)=14.4 Hz,
P1CH2P2), 38.1 (d, J(PC)=6.1 Hz, CH of C6H11), 30.8,
30.2 (both s, CH2 of C6H11), 30.5 (d, J(PC)=4.3 Hz,
CH2 of C6H11), 29.8 (d, J(PC)=4.1 Hz, CH2 of C6H11),
29.2 (d, J(PC)=10.0 Hz, CH2 of C6H11), 27.9 (d,
J(PC)=9.3 Hz, CH2 of C6H11), 27.2 (d, J(PC)=6.9
Hz, CH2 of C6H11), 27.0 (d, J(PC)=10.6 Hz, CH2 of
C6H11), 26.7, 26.4 (both s, CH2 of C6H11). 31P-NMR
(162.0 MHz, C6D6): l 25.8 (d, J(PP)=79.4 Hz, Cy2P),
15.4 (d, J(PP)=79.4 Hz, Ph2P).
[Ru(p2-OC6Cl5)2(s2-iPr2PCH2PPh2)] (10)
A solution of 112 mg (0.21 mmol) of 2 and 112 mg
(0.42 mmol) of pentachlorophenol in 10 ml of toluene
was stirred for 30 min at r.t. The solvent was evapo-
rated in vacuo, the residue was washed with 10 ml of
ethanol and 10 ml of pentane (0°C) and dried. Yellow
solid; yield 195 mg (98%), m.p. 224°C. Anal. Found: C,
39.58; H, 2.77. Calc. for C31H26Cl10O2P2Ru: C, 39.27;
1
H, 2.76%. H-NMR (400 MHz, CD2Cl2, 188 K): l 8.12
(m, 2H, C6H5), 7.46 (m, 3H, C6H5), 7.19–6.91 (m, 5H,
C6H5), 4.16, 3.36 (both m, 1H each, P1CH2P2), 2.74,
2.24 (both m, 1H each, PCHCH3), 1.41, 0.68 (both br
m, 6H each, PCHCH3). 1H-NMR (400 MHz, C6D6, 300
K): l 8.22 (m, 2H, C6H5), 7.28 (m, 3H, C6H5), 7.10 (m,
2H, C6H5), 6.85 (m, 3H, C6H5), 3.85, 3.53 (both m, 1H
each, P1CH2P2), 2.64, 1.78 (both m, 1H each,
PCHCH3), 1.43 (dd, J(PH)=16.8, J(HH)=7.3 Hz,
3H, PCHCH3), 1.19 (dd, J(PH)=15.1, J(HH)=7.0
Hz, 3H, PCHCH3), 0.64 (dd, J(PH)=11.7, J(HH)=
6.9 Hz, 3H, PCHCH3), 0.60 (dd, J(PH)=12.0,
J(HH)=7.5 Hz, 3H, PCHCH3). 13C-NMR (100.6
MHz, CD2Cl2, 188 K): l 161.9, 161.3 (both s, ipso-C of
C6Cl5), 137.2, 131.0 (both s, C6H5), 134.4 (br d,
J(PC)=12.3 Hz, C6H5), 130.4 (d, J(PC)=8.5 Hz,
C6H5), 129.9, 128.8, 128.1 (all s, C6H5), 129.5 (d,
J(PC)=12.3 Hz, C6H5), 127.5, 127.3, 126.7, 124.4,
123.8, 123.5, 117.0, 116.5, 113.5, 113.2 (all s, C6Cl5),
44.4 (m, P1CH2P2), 26.6 (d, J(PC)=20.0 Hz,
PCHCH3), 25.1 (d, J(PC)=19.1 Hz, PCHCH3), 18.5,
17.3, 16.9, 16.5 (all s, PCHCH3). 13C-NMR (100.6
MHz, C6D6, 300 K): l 163.8, 163.0 (both s, ipso-C of
C6Cl5), 134.4 (d, J(PC)=11.4 Hz, ortho-C of C6H5),
132.5 (d, J(PC)=48.0 Hz, ipso-C of C6H5), 131.7 (d,
J(PC)=53.0 Hz, ipso-C of C6H5), 131.5 (d, J(PC)=
2.9 Hz, para-C of C6H5), 130.8 (d, J(PC)=10.5 Hz,
ortho-C of C6H5), 129.6 (d, J(PC)=2.9 Hz, para-C of
C6H5), 128.6 (d, J(PC)=11.4 Hz, meta-C of C6H5),
128.0 (d, J(PC)=10.5 Hz, meta-C of C6H5), 125.6,
125.4, 118.4, 118.0, 116.4, 115.9 (all s, C6Cl5), 43.3 (dd,
J(PC)=22.9, J(PC)=19.1 Hz, P1CH2P2), 27.2, 25.1
(both d, J(PC)=20.0 Hz, PCHCH3), 19.5, 18.1, 17.9,
17.8 (all s, PCHCH3). 31P-NMR (162.0 MHz, C6D6,
300 K): l 37.2 (d, J(PP)=98.5 Hz, PiPr2), 15.4 (d,
J(PP)=98.5 Hz, PPh2).
3.10. Preparation of [Ru(p2-acac)2(s2-iPr2PCH2PPh2)]
(12)
A solution of 227 mg (0.24 mmol) of 10 in 10 ml of
toluene was treated with 48 mg (0.48 mmol) of acety-
lacetone and 69 mg (0.65 mmol) of Na2CO3 and then
heated for 1 h at 65°C. After cooling to r.t., the solvent
was evaporated in vacuo. The residue was dissolved in
5 ml of pentane, the solution was filtered and the
filtrate was brought to dryness in vacuo. Yellow solid;
yield 139 mg (96%), m.p. 152°C. Anal. Found: C, 56.02;
H, 6.86. Calc. for C29H40O4P2Ru: C, 56.58; H, 6.55%.
1
IR (CH2Cl2): w(acac) 1575, 1512 cm−1. H-NMR (200
MHz, CDCl3): l 7.85 (m, 2H, C6H5), 7.28 (m, 8H,
C6H5), 5.29, 4.98 (both s, 1H each, CH of acac),
4.14–3.78 (m, 2H, P1CH2P2), 2.42–1.91 (m, 2H,
PCHCH3), 1.90, 1.89, 1.82, 1.45 (all s, 3H each, CH3 of
acac), 1.24 (dd, J(PH)=10.6, J(HH)=7.7 Hz, 3H,
PCHCH3), 1.22 (dd, J(PH)=13.0, J(HH)=7.1 Hz,
3H, PCHCH3), 0.99 (dd, J(PH)=14.4, J(HH)=7.1
Hz, 3H, PCHCH3), 0.84 (dd, J(PH)=14.8, J(HH)=
7.1 Hz, 3H, PCHCH3). 31P-NMR (81.0 MHz, CDCl3):
l 34.9 (d, J(PP)=78.8 Hz, PiPr2), 17.0 (d, J(PP)=78.8
Hz, PPh2).
3.11. Preparation of
[Ru(OC6Cl5)2(CO)(s2-iPr2PCH2PPh2)] (13)
3.9. Preparation of
[Ru(p2-OC6Cl5)2(s2-Cy2PCH2PPh2)] (11)
A slow stream of CO was passed through a solution
of 100 mg (0.11 mmol) of 10 in 5 ml of benzene at r.t.
Stirring the solution for 1 h led to a change of color
from orange–red to yellow. The solvent was evapo-
rated in vacuo, the residue was washed with 5 ml of
pentane and dried. Yellow solid; yield 91 mg (85%),
m.p. 158°C. Anal. Found: C, 39.67; H, 2.89. Calc. for
C32H26Cl10O3P2Ru: C, 39.38; H, 2.68%. IR (CH2Cl2):
This was carried out analogously as described for 10,
using 135 mg (0.22 mmol) of 3 and 112 mg (0.44 mmol)
of pentachlorophenol as starting material. Yellow solid;
yield 195 mg (95%), m.p. 216°C. Anal. Found: C, 43.02;
H, 2.93. Calc. for C37H34Cl10O2P2Ru: C, 43.22; H,
1
3.33%. H-NMR (400 MHz, C6D6): l 7.76–6.66 (br m,

H. Werner et al. / Journal of Organometallic Chemistry 607 (2000) 182–193
191
1
w(CO) 1971 cm−1. H-NMR (400 MHz, C6D6, 295 K):
CNCCH3). 13C-NMR (100.6 MHz, C6D6): l 167.1 (d,
J(PC)=1.9 Hz, ipso-C of C6Cl5), 150.5 (d, J(PC)=
14.2 Hz, CNCCH3), 140.9 (dd, J(P1C)=17.1,
J(P2C)=3.8 Hz, CNCCH3), 133.6, 133.4, 129.3, 129.0
(all s, C6H5), 130.4, 127.9 (both s, C6Cl5), 128.8 (d,
J(PC)=7.6 Hz, C6H5), 116.9 (s, OC6Cl5), 56.6 (s,
CNCCH3), 30.2, 30.1 (both s, CNCCH3), 24.8 (dd,
J(P1C)=19.6, J(P2C)=6.2 Hz, PCHCH3), 19.7 (dd,
J(P1C)=35.3, J(P2C)=11.4 Hz, P1CH2P2), 18.0 (d,
J(PC)=1.9 Hz, PCHCH3), 17.9 (d, J(PC)=6.6 Hz,
PCHCH3). 31P-NMR (162.0 MHz, C6D6): l 3.6 (d,
J(PP)=69.1 Hz, PiPr2), −19.6 (d, J(PP)=69.1 Hz,
PPh2).
l 7.85 (br s, 2H, C6H5), 7.65 (m, 2H, C6H5), 6.98 (m,
6H, C6H5), 3.69, 2.98 (both m, 1H each, P1CH2P2), 2.55
(br s, 1H, PCHCH3), 1.64 (m, 1H, PCHCH3), 0.98 (m,
3H, PCHCH3), 0.84 (dd, J(PH)=17.6, J(HH)=7.3
Hz, 3H, PCHCH3), 0.79 (dd, J(PH)=17.3, J(HH)=
7.0 Hz, 3H, PCHCH3), 0.70 (dd, J(PH)=15.5,
1
J(HH)=6.7 Hz, 3H, PCHCH3). H-NMR (200 MHz,
toluene-d8, 325 K): l 7.76, 7.62 (both m, 2H each,
C6H5), 7.00 (m, 6H, C6H5), 3.80, 3.11 (both ddd,
J(P1H)=15.5, J(P2H)=10.5, J(HH)=10.0 Hz, 1H
each, P1CH2P2), 2.70, 1.79 (both m, 1H each,
PCHCH3), 1.08 (dd, J(PH)=17.9, J(HH)=7.3 Hz,
3H, PCHCH3), 0.98 (dd, J(PH)=16.5, J(HH)=6.2
Hz, 3H, PCHCH3), 0.90 (dd, J(PH)=17.3, J(HH)=
6.2 Hz, 3H, PCHCH3), 0.85 (dd, J(PH)=12.2,
J(HH)=6.9 Hz, 3H, PCHCH3). 13C-NMR (100.6
MHz, C6D6, 295 K): l 201.7 (dd, J(P1C)=18.3,
J(P2C)=15.3 Hz, CO), 161.6, (s, ipso-C of C6Cl5),
132.7 (br d, J(PC)=11.2 Hz, ortho-C of C6H5), 132.0
(d, J(PC)=3.0 Hz, para-C of C6H5), 131.9 (d, J(PC)=
11.2 Hz, ortho-C of C6H5), 131.7 (d, J(PC)=2.0 Hz,
para-C of C6H5), 130.3 (br s, ipso-C of C6H5), 129.3,
128.8 (both d, J(PC)=11.2 Hz, meta-C of C6H5),
128.1, 127.9, 117.1 (all s, C6Cl5), 41.3 (dd, J(P1C)=
28.5, J(P2C)=20.3 Hz, P1CH2P2), 28.2 (d, J(PC)=4.1
Hz, PCHCH3), 28.0 (d, J(PC)=3.1 Hz, PCHCH3),
25.4, 25.2 (both s, PCHCH3), 19.3 (d, J(PC)=4.1 Hz,
PCHCH3), 18.3 (s, PCHCH3). 31P-NMR (162.0 MHz,
C6D6, 295 K): l 28.5 (br s, PiPr2), 6.5 (br d, J(PP)=
69.5 Hz, PPh2). 31P-NMR (81.0 MHz, toluene-d8, 325
K): l 35.4 (d, J(PP)=71.3 Hz, PiPr2), 11.6 (d, J(PP)=
71.3 Hz, PPh2). 31P-NMR (81.0 MHz, toluene-d8, 245
K): l 43.2 (br s, PiPr2), 28.4 (d, J(PP)=77.5 Hz,
PiPr2), 13.9 (d, J(PP)=77.5 Hz, PPh2), 9.2 (br s, PPh2).
31P-NMR (81.0 MHz, toluene-d8, 217 K): l 43.2 (d,
J(PP)=68.7 Hz, PiPr2), 28.4 (d, J(PP)=75.0 Hz,
PiPr2), 13.8 (d, J(PP)=75.0 Hz, PPh2), 9.5 (d, J(PP)=
68.7 Hz, PPh2).
3.13. Preparation of
[RuCl(p3:p3-C10H16)(s2-iPr2PCH2PiPr2)]BF4 (16)
A suspension of 100 mg (0.16 mmol) of 15 in 10 ml
of acetone was treated with a solution of 63 mg (0.32
mmol) of AgBF4 in 3 ml of acetone and stirred for 20
min at r.t. The reaction mixture was filtered and to the
filtrate 79.5 mg (0.32 mmol) of iPr2PCH2PiPr2 was
added. After stirring the solution for 20 min, the sol-
vent was evaporated in vacuo, the residue was washed
with 2 ml of pentane and dried. Orange solid; yield 160
mg (82%), m.p. 178°C (dec.). Conductivity: \ 75.4 cm2
V−1 mol−1. Anal. Found: C, 44.97; H, 7.34. Calc. for
1
C23H46BClF4P2Ru: C, 45.44; H, 7.63%. H-NMR (200
MHz, CD2Cl2): l 4.59, 4.45 (both m, 1H each, H1 and
H9), 3.92 (d, J(PH)=3.7 Hz, 1H, H2 or H10), 3.66 (m,
2H, H3 and H8), 3.32 (m, 1H, H2 or H10), 3.17–2.63 (m,
6H, PCHCH3 and PCH2P), 2.56–2.43 (m, 4H, H4–7),
2.11 (s, 6H, CH3 of C10H16), 1.80–1.02 (m, 24H,
PCHCH3). 13C-NMR (50.3 MHz, CD2Cl2): l 108.4 (s,
C2 and C7), 86.1 (s, C3 and C6), 66.1, 63.0 (both s, C1
and C8), 38.4, 29.5 (both s, C4 and C5), 35.5 (d,
J(PC)=16.6 Hz, PCHCH3), 34.3 (dd, J(PC)=15.7
and 4.6 Hz, PCHCH3), 32.1 (t, J(PC)=24.0 Hz,
PCH2P), 30.8 (s, PCHCH3), 28.8 (dd, J(PC)=13.9 and
6.5 Hz, PCHCH3), 27.7 (d, J(PC)=12.0 Hz,
PCHCH3), 21.7, 21.6, 21.3, 20.8, 20.3, 20.1, 19.9, 19.8,
19.6, 19.4, 18.8, 18.7 (PCHCH3 and CH3 of C10H16).
31P-NMR (81.0 MHz, CD2Cl2): l −14.2, −20.0 (both
d, J(PP)=48.3 Hz). For assignment of protons and
carbon atoms see Fig. 4.
3.12. Preparation of
[Ru(OC6Cl5)2(CNtBu)3(s1-Ph2PCH2PiPr2)] (14)
A solution of 110 mg (0.12 mmol) of 10 in 5 ml of
toluene was treated with an excess (ca. 0.50 mmol) of
CNtBu. After stirring for 1 h, the solvent was evapo-
rated in vacuo, the residue was washed with 5 ml of
pentane and dried. Yellow solid; yield 122 mg (87%),
m.p. 135°C. Anal. Found: C, 46.14; H, 4.23; N, 3.55.
Calc. for C46H53Cl10N3O3P2Ru: C, 45.53; H, 4.40, N,
3.46%. IR (CH2Cl2): w(CN) 2161, 2136 cm−1. 1H-NMR
(400 MHz, C6D6): l 7.75, 7.08 (both m, 4H each,
C6H5), 6.99 (m, 2H, C6H5), 3.64 (dd, J(P1H)=6.7,
J(P2H)=3.2 Hz, 2H, P1CH2P2), 3.12 (m, 2H,
PCHCH3), 1.50 (dd, J(PH)=14.1, J(HH)=7.0 Hz,
12H, PCHCH3), 1.21 (s, 18H, CNCCH3), 1.01 (s, 9H,
3.14. Preparation of
[RuCl2(p3:p3-C10H16)(s-P-iPr2PCH2AstBu2)] (17)
A solution of 154 mg (0.25 mmol) of 15 in 10 ml of
CH2Cl2 was treated at −78°C with a solution of 164
mg (0.51 mmol) of iPr2PCH2AstBu2 in 5 ml of CH2Cl2.
After stirring for 10 min, the solution was warmed to
r.t. and then the solvent was evaporated. The residue
was washed with 5 ml of pentane and dried. Pale red
solid; yield 304 mg (97%), m.p. 92°C. Anal. Found: C,

192
H. Werner et al. / Journal of Organometallic Chemistry 607 (2000) 182–193
by direct methods (SHELXS-86); atomic coordinates
were refined by full-matrix least-squares against Fo2
(307 parameters, SHELXL-93). The positions of H1a,
H1b, H2a, H2b, H4a, H4b, H6a, H6b, H8a and H8b
were found in a final difference Fourier synthesis and
were refined isotropically with fixed distance (CꢀH
,
0.93 A). The positions of all other hydrogen atoms
were calculated according to ideal geometry. R1=
0.0397, wR2=0.0920 for 4497 observed reflections
[I\2|(I)], R1=0.0479, wR2=0.0986 for all 5163 data
reflections; reflex to parameter ratio 16.8; residual elec-
−3
,
tron density +0.816/−1.067 e A
.
Fig. 4. Assignment of protons and carbon atoms of the octadienediyl
ligand of compounds 16 and 17.
3.16. Crystal structure analysis of 7
Single crystals were grown from toluene. Crystal
data (from 5000 reflections with 2°BqB26°): mono-
clinic, space group I2/m (no. 12), a=10.441(2), b=
47.53; H, 7.67. Calc. for C25H50AsCl2PRu: C, 47.77;
H, 8.02%. H-NMR (400 MHz, C6D6): l 5.30 (m, 2H,
1
H1 and H9), 4.77 (d, J(PH)=7.6 Hz, 2H, H3 and H8),
3.59 (d, J(PH)=2.8 Hz, 2H, H2 and H10), 3.12 (m,
2H, H5 and H7), 2.67 (m, 2H, PCHCH3), 2.56, 2.29
(both dd, J(PH)=14.5, J(HH)=6.8 Hz, 1H each,
PCH2As), 2.20 (s, 6H, CH3 of C10H16), 2.13 (m, 2H,
H4 and H6), 1.64 (dd, J(PH)=14.4, J(HH)=7.2 Hz,
3H, PCHCH3), 1.53 (dd, J(PH)=11.6, J(HH)=6.8
Hz, 3H, PCHCH3), 1.52 (dd, J(PH)=14.2, J(HH)=
7.2 Hz, 3H, PCHCH3), 1.41 (dd, J(PH)=14.2,
J(HH)=7.2 Hz, 3H, PCHCH3), 1.18, 1.17 (both s, 9H
each, AsCCH3). 13C-NMR (100.6 MHz, C6D6): l
124.2 (s, C2 and C7), 108.3 (s, C3 and C6), 62.9 (d,
J(PC)=5.0 Hz, C1 and C8), 36.4 (s, C4 and C5), 36.3
(d, J(PC)=3.0 Hz, AsCCH3), 34.4 (d, J(PC)=1.7
Hz, AsCCH3), 30.6 (d, J(PC)=18.7 Hz, PCHCH3),
30.4, 30.2 (both s, AsCCH3), 29.3 (d, J(PC)=20.6 Hz,
PCHCH3), 21.0 (s, CH3 of C10H16), 19.9 (d, J(PC)=
7.2 Hz, PCHCH3), 19.5, 19.0, 18.4 (all s, PCHCH3),
12.7 (d, J(PC)=13.1 Hz, PCH2As). 31P-NMR (162.0
MHz, C6D6): l 25.0 (s). For assignment of protons
and carbon atoms see Fig. 4.
,
14.452(3), c=16.380(3) A, i=108.27(2)°, V=
3
2347.1(7) A ; Z=2, Dcalc=1.296 g cm−3, v=0.522
,
mm−1. Crystal size 0.2×0.2×0.2 mm3. Stoe IPDS
,
diffractometer, Mo–Ka radiation (0.71073 A), graphite
monochromator, T=173(2) K, b-scan, max. 2q=52°;
15 607 reflections scanned, 2397 reflections indepen-
dent, 2396 included in the dataset; intensity data cor-
rected for Lorentz and polarization effects. The
structure was solved by direct methods (SHELXS-86);
atomic coordinates were refined by full-matrix least-
squares against F2o (129 parameters, SHELXL-93). The
asymmetric unit contains only one-fourth of 7 with the
ruthenium atom on the centre of symmetry. The com-
plete molecule is generated by applying the symmetry
operations c1: −x, −y, −z; c2: −x, y, −z and
c3: x, −y, z. The positions of the hydrogen atoms
were calculated according to ideal geometry. The
asymmetric unit contains one-fourth of a solvent
molecule (toluene) which was refined isotropically with
restraints. The highest peak of the final Fourier syn-
thesis is located near to this solvent molecule. R1=
0.0448, wR2=0.1190 for 1872 observed reflections
[I\2|(I)], R1=0.0607, wR2=0.1273 for all 2396 data
3.15. Crystal structure analysis of 2
reflections; reflex to parameter ratio 18.6; residual elec-
−3
,
tron density +1.108/−0.974 e A
.
Single crystals were grown from ether. Crystal data
(from 25 reflections with 7BqB25°): triclinic, space
(
group P1 (no. 2), a=8.861(7), b=9.796(9), c=
4. Supplementary material
,
15.12(1) A, h=80.47(6), i=81.81(6), k=85.58(6)°,
V=1279(2) A ; Z=2, Dcalc=1.370 g cm−3, v=0.741
3
,
Detailed crystallographic data (excluding structure
factors) for the structure of 2 and 7 have been de-
posited with the Cambridge Crystallographic Data
Centre as supplementary publication no. 141732 (2)
and 141733 (7). Copies of the data can be obtained
free of charge on application to: The Director, CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (fax: +44-
1223-336033; e-mail: deposit@chemcrys.cam.ac.uk;
www: http://www.ccdc.cam.ac.uk).
mm−1. Crystal size 0.2×0.2×0.1 mm. Enraf–Nonius
,
CAD4 diffractometer, Mo–Ka radiation (0.71073 A),
graphite monochromator, T=293(2) K, ꢀ–q scan,
max. 2q=50°; 5534 reflections scanned, 5163 reflec-
tions independent, 5163 included in dataset; intensity
data corrected for Lorentz and polarization effects,
empirical absorption correction applied (C-scans, min-
imum transmission 91.91%). The structure was solved

H. Werner et al. / Journal of Organometallic Chemistry 607 (2000) 182–193
193
[3] H. Werner, M. Manger, U. Schmidt, M. Laubender, B. Webern-
do¨rfer, Organometallics 17 (1998) 2619.
Acknowledgements
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[5] G. Fries, M. Manger, B. Weberndo¨rfer, H. Werner, XVIIIth
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This work was supported by the Deutsche
Forschungsgemeinschaft (SFB 347) and the Fonds der
Chemischen Industrie. We thank S. Link for commited
collaboration during an advanced study course. We
also thank Dr W. Buchner and M.-L. Scha¨fer for NMR
measurements, Dr R. Bertermann for the NMR simula-
tion, R. Schedl and C.P. Kneis for elemental analysis
and DTA measurements. Generous support by the
BASF AG and the Degussa-Hu¨ls AG is also gratefully
acknowledged.
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