Different reactivity of the Ru-O bond in the chelated [(methoxyethyl)diphenylphosphine]ruthenium(II) complexes [(η6-C6Me6)Ru(P∩O)X][BR 4] in dependence on X = Cl and CH3

Article abstract of DOI:10.1016/S0022-328X(97)00754-7

Treatment of the starting complexes [(η⁶-C₆Me₆)Ru(P～O)X₂] (X = Cl (1), CH₃ (2); P～O = η¹ (P)-coordinated ether-phosphine ligand Ph₂PCH₂CH₂OCH₃) with NaBPh₄ and HBF₄, respectively, lead to the chelated complexes [(η⁶-C₆Me₆)Ru(P^∩O)X][BR ₄] (X = Cl (3a), CH₃ (3b); R = Ph (3a), F (3b); P^∩O = η² (O,P)-coordinated ligand). The rupture of the Ru-O bond in 3a,b with carbon monoxide and acetonitrile results in the formation of the corresponding complexes [(η⁶-C₆Me₆)Ru(CO)(P～O)X][BR ₄] (4a,b) and [(η⁶-C₆Me₆)Ru(CH₃CN)(P～O)X] [BR₄] (5a,b). The structure of 4a was determined by single-crystal X-ray diffraction. In a similar way the cleavage of the Ru-O bond is achieved when 3a is reacted with tert-butyl isocyanide and 3b with ethene to give the adducts [(η⁶-C₆Me₆)Ru(CN ^tBu)(P～O)Cl][BPh₄] (6a) and [(η⁶-C₆Me₆)Ru(η²-C ₂H₄)(CH₃)(P～O)][BF₄] (7b). All compounds are obtained in excellent yields and under mild conditions.

Full text of DOI:10.1016/S0022-328X(97)00754-7

Journal of Organometallic Chemistry 555 (1998) 247–253
Different reactivity of the Ru–O bond in the chelated
[(methoxyethyl)diphenylphosphine]ruthenium(II) complexes
[(p6-C6Me6)Ru(PSO)X][BR4] in dependence on X=Cl and CH3
Ekkehard Lindner *, Stefan Pautz, Riad Fawzi, Manfred Steimann
Institut fu¨r Anorganische Chemie der Uni6ersita¨t Tu¨bingen, Auf der Morgenstelle 18, D-72076, Tu¨bingen, Deutschland
Received 30 September 1997; received in revised form 12 November 1997
Abstract
Treatment of the starting complexes [(p6-C6Me6)Ru(P~O)X2] (X=Cl (1), CH3 (2); P~O=p1 (P)-coordinated ether-phosphine
ligand Ph2PCH2CH2OCH3) with NaBPh4 and HBF4, respectively, lead to the chelated complexes [(p6-C6Me6)Ru(PSO)X][BR4]
(X=Cl (3a), CH3 (3b); R=Ph (3a), F (3b); PSO=p2 (O,P)-coordinated ligand). The rupture of the Ru–O bond in 3a,b with
carbon monoxide and acetonitrile results in the formation of the corresponding complexes [(p6-C6Me6)Ru(CO)(P~O)X][BR4]
(4a,b) and [(p6-C6Me6)Ru(CH3CN)(P~O)X] [BR4] (5a,b). The structure of 4a was determined by single-crystal X-ray diffraction.
In a similar way the cleavage of the Ru–O bond is achieved when 3a is reacted with tert-butyl isocyanide and 3b with ethene to
give the adducts [(p6-C6Me6)Ru(CNtBu)(P~O)Cl][BPh4] (6a) and [(p6-C6Me6)Ru(p2-C2H4)(CH3)(P~O)][BF4] (7b). All compounds
are obtained in excellent yields and under mild conditions. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Ruthenium complexes; Ether–phosphine ligands; Coordinated ligand
1. Introduction
Therefore such ligands may both enhance the reactivity
and avoid decomposition of complexes [2,4]. In a pre-
ceding investigation we reported on the synthesis of the
The appropriation of empty coordination sites in the
form of coordinatively unsaturated and hence very
reactive metal complexes represents an important step
in stoichiometric and catalytic reactions. A marked
progress in the stabilization of such intermediates was
achieved by the introduction of so-called hemilabile
ligands [1–3]. These systems are provided with a
strongly coordinating atom and additionally with a
hard donor site forming only a weak contact to the
metal center. In this context we investigated ruthenium,
rhodium, and palladium complexes containing ether-
phosphines (O,P) acting as monodentate (P~O) and
bidentate (PSO) ligands (P~O=p1 (P)-coordinated lig-
and; PSO=p2 (O,P)-coordinated ligand) [2,4]. Due to
the hemilabile character, the ether-oxygen atom is able
to generate or to occupy vacant coordination sites.
complexes
[(p6-C6Me6)RuH(PSO)][BF4]
(PSO=
diphenyl(ether-phosphine)) and their behavior toward
small molecules in dependence on the employed ether
moiety [5]. In this work we demonstrate the influence of
the ligand X on the reactivity of the Ru–O bond in
reactions of the p2 (O,P)-chelated complexes [(p6-
C6Me6)Ru(PSO)X][BR4] (X=Cl (a), CH3 (b); R=Ph
(a), F (b)) with small molecules such as carbon monox-
ide, acetonitrile, tert-butyl isocyanide, and ethene.
2. Results and discussion
2.1. Synthesis of the p2 (O,P)-chelated complexes
[(p6-C6Me6)Ru(PSO)X][BR4] (3a,b)
One of both starting complexes (2) (Scheme 1) is
* Corresponding author. Tel.: +49 707 1295306.
accessible by treatment of the previously described
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(97)00754-7

248
E. Lindner et al. / Journal of Organometallic Chemistry 555 (1998) 247–253
Scheme 1. Reaction scheme showing the production of the chelates 3a,b from [{(p6-C6Me6)RuCl2}2], followed by further reaction to form the
complexes 4a,b, 5a,b, 6a and 7b.
shifted to lower field as well. Typical doublets at 4.7
dichlororuthenium complex 1 [5] with two equivalents
of methyl lithium in THF [6].
ppm (2J(PC)=15.0 Hz) in the 13C{1H} and at −0.4
1
ppm (3J(PH)=7.2 Hz) in the H-NMR spectra of 3b
The intramolecular coordination of the ether-moiety
succeeded by reaction of 1 and 2 with NaBPh4 and
HBF4, respectively, leading to the chelates 3a,b (Scheme
1). Whereas red 3a represents a stable compound, the
dark yellow congener 3b decomposes even under an
atmosphere of argon. The 31P{1H} NMR spectra of
3a,b display each a singlet at 51.2 and 58.3 ppm. Due to
the ring contribution DR [7] this resonance is shifted to
lower field compared to the corresponding 31P signal of
1 and 2. A further evidence for the existence of a p2
(O,P)-coordination mode in 3a,b can be derived from
the 13C{1H} NMR spectra. The signals of the carbon
atoms in the h-position to the ether-oxygen atoms are
are attributed to the metal bound methyl group.
It should be mentioned that the comparable com-
plexes [(p6-arene)RuCl(PSO)][BPh4] (arene=cymene,
mesitylene) are accessible in a similar manner [8]. How-
ever, these species release the arene moiety when re-
acted with carbon monoxide.
2.2. Reacti6ity of 3a,b toward carbon monoxide,
acetonitrile, isocyanide, and ethene
In order to get an insight into the reactivity of the
Ru–O bond the behavior of 3a,b toward carbon
monoxide, acetonitrile, and ethene was verified.

E. Lindner et al. / Journal of Organometallic Chemistry 555 (1998) 247–253
249
When a dichloromethane solution of 3a,b is stirred
under an atmosphere of carbon monoxide with cleav-
age of the Ru–O bonds the yellow carbonyl complexes
4a,b (Scheme 1) are obtained, which dissolve readily in
polar organic solvents. While the formation of 4b is
quantitative within 30 min, the completion of the reac-
tion in the case of 4a requires 16 h. The 31P{1H} and
13C{1H} NMR spectra are in accordance with a p1
(P)-coordination of the ether-phosphines. Moreover the
13C{1H} NMR spectra of 4a,b reveal each a low inten-
sity doublet at 196.7 and 200.6 ppm which is assigned
to the carbonyl groups. The IR spectra of 4a,b exhibit
typical absorptions at 2001 and 1961 cm−1 for the CꢀO
stretching vibrations [9]. Remarkably the CO band of
4a appears at higher energy compared to 4b. This fact
points to an increased electron density at the ruthenium
center in 4b.
Ru–O bond takes place and the yellow adducts [(p6-
C6Me6)Ru(L)(P~O)X][BR4] (5a,b, 6a: L=CH3CN, t-
BuNC, Scheme 1) are formed. In contrast to the
complexes [(p6-arene)RuCl(PSO)][PF6] [10] which need
an excess of the ligand L for a complete formation of
the addition products, in the case of 5a and 6a a
quantitative reaction was achieved with equimolar
amounts of L. Moreover an equilibrium between the
starting chelate and the final adduct was not observed
in the present case which is in contrast to the observa-
tions of Demerseman [10]. However, 5a eliminates ace-
tonitrile in the solid state. Within a week 3a is reformed
in a yield of 30%.
A single 31P resonance in the 31P{1H} NMR spectra
of 5a,b (l 27.1 (5a), l 36.4 (5b)) and 6a (l 34.0) points
to p1 (P)-coordinated ether-phosphines. Compared to
the educts 3a,b these singlets are shifted characteristi-
cally to higher field [2]b; [7]. Besides the typical 13C
signals which are attributed to the hexamethylbenzene
and phosphine ligands the 13C{1H} NMR spectra of
5a,b and 6a show resonances for the nitrile (l 124.7
(5b)) and isocyanide (l 142.2) carbon atoms which are
slightly shifted to lower and higher field, respectively,
compared to those of the uncoordinated ligands. These
data correspond well with related results reported in the
literature [11].
For a full characterization of 4a a crystal structure
determination was performed. The ORTEP-drawing is
depicted in Fig. 1. Complex 4a adopts a three-legged
piano stool configuration which is evidenced by near-
90° angles between P(1)–Ru(1)–Cl(1), C(52)–Ru(1)–
P(1), and C(52)–Ru(1)–C(1), respectively. The
Ru–C–O unit shows the typical arrangement with
˚
bond lengths Ru(1)–C(52)=1.878 (4) A and Ru(1)–
˚
P(1)=2.3365 (9) A which are in good agreement with
the corresponding distances in the complexes
The action of ethylene on the (ether-phos-
phine)methylruthenium(II) complex 3b affords the light
yellow, thermally unstable p2-ethene complex [(p6-
C6Me6)Ru(p2-C2H4) (CH3)(P~O)][BF4] (7b) which dis-
solves readily in polar solvents, because of its ionic
structure. Remarkably the Ru–O bond cleavage fails
even at prolonged reaction times if the same reaction is
carried out with 3a. The 31P{1H} NMR spectrum of 7b
is in accordance with a p1 (P)-coordinated phosphine.
Two singlets at 51.5 and 46.2 ppm in the 13C{1H}
NMR spectrum of 7b are ascribed to the ethylene
ligand. This result demonstrates that the rotation of
C2H4 is slow with respect to the NMR time scale. Each
[Cp*Ru(CO)(PSO)][BPh4]
(PPh3)[BPh4] [4]b.
and
[Cp*Ru(CO)(P~O)
If dichloromethane solutions of the O,P-chelates 3a,b
are treated with acetonitrile and additionally 3a also
with tert-butyl isocyanide a spontaneous rupture of the
1
a doublet in the 13C{1H} and the H-NMR spectrum is
assigned to the CH3 group [9].
Whereas
the
hydride
complexes
[(p6-
C6Me6)RuH(PSO)][BF4] [5] exhibit a considerable cata-
lytic activity in the ring opening polymerization of
norbornene, the chelates 3a,b lead only to poor yields
of polynorbornene in this reaction.
3. Conclusions
A comparison of the related O,P-chelated complexes
3a,b shows a considerable dependence of the reactivity
of the Ru–O bond on the employed ligand X. This is
reflected in the behavior of 3a,b toward the y-acceptor
ligands carbon monoxide and ethene. In contrast to the
facile formation of the CO complex 4b, the reaction
˚
Fig. 1. ORTEP plot of complex 4a. Selected interatomic distances (A)
and angles (°): Ru(1)–C(52) 1.878(4); Ru(1)–Cl(1) 2.3837(10);
Ru(1)–P(1) 2.3365(9); O(1)–C(52) 1.111(4); C(52)–Ru(1)–P(1)
90.27(10); P(1)–Ru(1)–Cl(1) 86.67(3); C(52)–Ru(1)–Cl(1) 92.71(11);
O(1)–C(52)–Ru(1) 171.7(3).

250
E. Lindner et al. / Journal of Organometallic Chemistry 555 (1998) 247–253
between 3a and CO requires a longer time under the
same conditions (temperature, CO pressure). Even a
bigger difference is observed when 3a,b are treated with
ethene. Only in the case of 3b a Ru–O bond rupture
takes place and the empty coordination site is occupied
by this incoming ligand. No difference is established
when 3a,b is reacted with ligands which are provided
with predominantly |-donor properties which was
proved with the examples of acetonitrile and tert-butyl
isonitrile. In the case of y-acceptor ligands the different
reactivity of the Ru–O bond can be explained with an
increased electron density in the methyl containing
complex 3b. This is indicated by the CO stretching
frequencies in the IR spectra of 4a,b.
538 [M+]. Anal. Calc. for C29H41OPRu (537.68): C,
64.78%; H, 7.69%; Ru, 18.80%. Found: C, 64.49%; H,
7.64%; Ru, 18.72%. 31P{1H} NMR (101.25 MHz, C6D6,
22°C): l=43.6 (s). 13C{1H} NMR (62.90 MHz, C6D6,
2
22°C): l=138.2–128.0 (m, C–Ph), 97.2 (d, J(PC)=
6.3 Hz, C6Me6), 70.1 (s, CH2O), 58.2 (s, OCH3), 29.2
1
(d, J(PC)=25.2 Hz, PCH2), 14.8 (s, C6Me6), −2.5 (d,
2J(PC)=18.9 Hz, RuCH3). 1H-NMR (250.13 MHz,
C6D6, 22°C): l= −0.1 (d, 3J(PH)=5.7 Hz, 6H,
RuCH3).
4.3. Chloro(p6-hexamethylbenzene)
[(methoxyethyl)diphenylphosphine-O,P]ruthenium(II)
tetraphenylborate (3a)
A mixture of 800 mg (1.38 mmol) of 1 and 473 mg
(1.38 mmol) of NaBPh4 in 50 ml of CH2Cl2 was stirred
for 16 h at room temperature. The solvent was removed
under reduced pressure. The residue was redissolved in
20 ml of CH2Cl2 and the solution was filtered (G4) to
separate NaCl. The solvent was evaporated to dryness
in vacuo and the residue was washed with 20 ml of
n-hexane to give a red precipitate which was collected
by filtration (G3) and dried under reduced pressure:
yield 1.19 g (90%); mp. 101°C (dec); MS (FD, 60°C):
m/e 543 [M+-BPh4]. Anal. Calc. for C51H55BClOPRu
(862.30): C, 71.03%; H, 6.43%; Cl, 4.11%; Ru, 11.72%.
Found: C, 70.98%; H, 6.47%; Cl, 4.11%; Ru, 12.03%.
31P{1H} NMR (101.25 MHz, CD2Cl2, 22°C): l=51.2
(s). 13C{1H} NMR (62.90 MHz, CD2Cl2, 22°C): l=
163.9 (q, 1J(CB)=49.1 Hz, ipso-C of BPh4), 135.9–
121.8 (m, C–Ph), 97.9 (d, 2J(PC)=2.1 Hz, C6Me6),
4. Experimental section
4.1. General procedures
All manipulations were carried out under an atmo-
sphere of argon by use of standard Schlenk techniques.
Solvents were dried over appropriate reagents and
stored under argon. IR data were obtained with a
Bruker IFS 48 FT–IR instrument. FD mass spectra
were taken on a Finnigan MAT 711 A instrument (8
kV, 60°C), modified by AMD; FAB mass spectra were
recorded on a Finnigan MAT TSQ 70 (10 kV, 50°C).
Elemental analyses were performed with a Carlo Erba
1106 analyzer; Cl and F analyses were carried out
according to Scho¨niger [12], and were analyzed as
described by Dirscherl and Erne [13], and Brunisholz
and Michot [14], respectively. Ru was analyzed accord-
ing to the literature [15]. 1H, 31P{1H}, and 13C{1H}
NMR spectra were recorded on a Bruker DRX 250
spectrometer at 250.13, 101.25, and 62.90 MHz, respec-
1
76.5 (s, CH2O), 66.7 (s, OCH3), 29.1 (d, J(PC)=27.7
Hz, PCH2), 15.5 (s, C6Me6).
4.4. p6-Hexamethylbenzene[(methoxyethyl)
diphenylphosphine-O,P](methyl)ruthenium(II)
tetrafluoroborate (3b)
1
tively. H and 13C chemical shifts were measured rela-
tive to partially deuterated solvent peaks and to
deuterated solvent peaks, respectively. 31P chemical
shifts were measured relative to 85% H3PO4 (l=0).
HBF4 was used as a 54 wt% solution in diethyl ether
and methyl lithium as 1.6N solution in diethyl ether.
Ph2PCH2CH2OCH3 [16] and the starting complex 1 [5]
were prepared as previously described.
A solution of 2 (200 mg, 0.37 mmol) in 10 ml of
CH2Cl2 was treated with HBF4 (0.37 mmol) at room
temperature. The yellow color of the solution turns
spontaneously to orange and the formation of methane
is observed. After 15 min of stirring the solvent was
removed under reduced pressure. The residue was
washed with 10 ml of n-hexane to give a dark yellow
precipitate, which was collected by filtration (G3) and
dried in vacuo to yield 215 mg (95%) of 3b; mp. 78°C
(dec); MS (FD, 60°C): m/e 523 [M+-BF4]. Anal. Calc.
for C28H38BF4OPRu (609.45): C, 55.18%; H, 6.28%; F,
12.47%; Ru, 16.58%. Found: C, 54.83%; H, 6.30; F,
12.38%; Ru, 16.35%. 31P{1H} NMR (101.25 MHz,
CD2Cl2, 22°C): l=58.3 (s). 13C{1H} NMR (62.90
MHz, CD2Cl2, 22°C): l=132.9–128.9 (m, C–Ph), 97.8
4.2. p6-Hexamethylbenzene[(methoxyethyl)
diphenylphosphine-P](dimethyl)ruthenium(II) (2)
A suspension of 1 (675 mg, 1.16 mmol) in 40 ml of
THF was treated with methyl lithium (2.32 mmol) and
stirred for 15 min at room temperature. The resulting
yellow solution was transferred to a neutral alumina
column (length of column: 5 cm) and eluted with THF.
The solvent was removed completely and the residue
was dried in vacuo to give 565 mg (90%) of 2 as a
yellow powder; mp. 130°C (dec); MS (FD, 60°C): m/e
2
(d, J(PC)=3.0 Hz, C6Me6), 78.1 (s, CH2O), 65.3 (s,
OCH3), 29.0 (d, 1J(PC)=26.0 Hz, PCH2), 15.3 (s,

E. Lindner et al. / Journal of Organometallic Chemistry 555 (1998) 247–253
251
2
1
Table 1
C6Me6), 4.7 (d, J(PC)=15.0 Hz, RuCH3). H-NMR
Crystal data and refinement details for 4a
3
(250.13 MHz, CD2Cl2, 22°C): l= −0.4 (d, J(PH)=
7.2 Hz, 3H, RuCH3).
Compound 4a
4.5. Carbonyl(chloro)(p6-hexamethylbenzene)
[(methoxyethyl)diphenylphosphine-P]ruthenium(II)
tetraphenylborate (4a)
Formula
FW
Color
C52H55BClO2PRu
890.3
Yellow cubes
0.19×0.15×0.10
Monoclinic
P21/n
11.693 (3)
21.279 (5)
17.934 (3)
99.62 (2)
4400 (2)
4
1.344
−100
1856
0.490
4–50
15 472
7743
524
Crystal dimensions
Crystal system
Space group
A solution of 3a (110 mg, 0.13 mmol) in 10 ml of
CH2Cl2 was treated with carbon monoxide (1 bar) at
room temperature. After 16 h the color of the orange
solution changed to yellow. The solvent was removed
and the residue was washed with 10 ml of n-hexane to
give a yellow precipitate which was collected by filtra-
tion (G3) and dried under reduced pressure to yield 113
mg (100%) of 4a; mp. 156°C; MS (FD, 60°C): m/e 571
[M+-BPh4]. Anal. Calc. for C52H55BClO2PRu (890.31):
C, 70.15%; H, 6.23%; Cl, 3.98%; Ru, 11.35%. Found:
C, 69.81%; H, 6.20%; Cl, 4.00%; Ru, 11.58%. IR (KBr):
˚
a (A)
˚
b (A)
˚
c (A)
i (°)
V (A )
3
˚
Z
Calc. density (g cm−3
T (°C)
)
F(000), e
v(Mo–Kh), mm−1
2q limits (°)
No. of reflections measured
No. of unique data with I]2|(I)
No. of variables
w(CO)=2001 (vs) cm−1
.
31P{1H} NMR (101.25 MHz,
CD2Cl2, 22°C): l=35.7 (s). 13C{1H} NMR (62.90
S
1.14
0.033
0.061
2
MHz, CD2Cl2, 22°C): l=196.7 (d, J(PC)=25.1 Hz,
aR1
bwR2
CO), 164.0 (q, 1J(CB)=50.3 Hz, ipso-C of BPh4),
137.8–121.8 (m, C–Ph), 113.5 (s, C6Me6), 66.9 (s,
CH2O), 58.1 (s, OCH3), 30.6 (d, 1J(PC)=37.7 Hz,
PCH2), 16.0 (s, C6Me6).
a R1=SꢀF0ꢁ−ꢁFcꢀ/SꢁF0ꢀ.
b wR2={S[w(F02−Fc2)2]/S[w(F20)2]}0.5
.
4.6. Carbonyl(p6-hexamethylbenzene)
[(methoxyethyl)diphenylphosphine-P]
(methyl)ruthenium(II) tetrafluoroborate (4b)
stirring the solution was evaporated to dryness under
reduced pressure and the residue was washed with 10
ml of n-hexane. The pale yellow precipitate was col-
lected by filtration (G3) and dried in vacuo to yield 105
mg (100%) of 5a; mp. 66°C (dec); MS (FD, 60°C): m/e
Complex 4b was synthesized and worked up in the
same way as 4a by reacting a solution of 100 mg (0.16
mmol) of 3b in 10 ml of CH2Cl2 with carbon monoxide
(1 bar) for 30 min: yield 104 mg (100%); mp. 63°C
(dec); MS (FAB, 50°C): m/e 551 [M+-BF4]. Anal. Calc.
for C29H38BF4O2PRu (637.46): C, 54.64%; H, 6.01%; F,
11.92%; Ru, 15.86%. Found: C, 54.54%; H, 5.98%; F,
12.03%; Ru, 16.11%. IR (KBr): w(CO)=1961 (vs)
543
[M+-BPh4–CH3CN].
Anal.
Calc.
for
C53H58BClNOPRu (903.35): C, 70.47%; H, 6.47%; Cl,
3.93%; N, 1.55%; Ru, 11.19%. Found: C, 70.26%; H,
6.71%; Cl, 4.23%; N, 1.60%; Ru, 11.06%. 31P{1H}
NMR (101.25 MHz, CD2Cl2, 22°C): l=27.1 (s).
13C{1H} NMR (62.90 MHz, CD2Cl2, 22°C): l=164.3
1
(q, J(CB)=49.2 Hz, ipso-C of BPh4), 136.1–122.0 (m,
cm−1
.
31P{1H} NMR (101.25 MHz, CD2Cl2, 22°C):
C–Ph and CH3CN), 100.4 (d, 2J(PC)=2.7 Hz,
C6Me6), 67.8 (d, 2J(PC)=3.4 Hz, CH2O), 58.3 (s,
OCH3), 28.4 (d, 1J(PC)=29.0 Hz, PCH2), 15.8 (s,
C6Me6), 3.6 (s, CH3CN).
l=39.5 (s). 13C{1H} NMR (62.90 MHz, CD2Cl2,
22°C): l=200.6 (d, 2J(PC)=35.1 Hz, CO), 133.0–
128.4 (m, C–Ph), 114.3 (d, J(PC)=6.3 Hz, C6Me6),
67.2 (s, CH2O), 58.3 (s, OCH3), 30.2 (d, J(PC)=33.0
Hz, PCH2), 15.9 (s, C6Me6), −9.0 (d, J(PC)=10.0
Hz, RuCH3). H-NMR (250.13 MHz, CD2Cl2, 22°C):
l=0.4 (d, J(PH)=4.5 Hz, 3H, RuCH3).
2
1
2
4.8. Acetonitrile(p6-hexamethylbenzene)
[(methoxyethyl)diphenylphosphine-P]
(methyl)ruthenium(II) tetrafluoroborate (5b)
1
3
4.7. Acetonitrile(chloro)(p6-hexamethylbenzene)
[(methoxyethyl)diphenylphosphine-P]ruthenium(II)
tetraphenylborate (5a)
5b was prepared and worked up analogously to 5a by
treating a solution of 120 mg (0.2 mmol) of 3b in 10 ml
of CH2Cl2 with 8.1 mg (0.2 mmol) of CH3CN: yield 128
mg (100%); mp. 51°C (dec); MS (FAB, 50°C): m/e 564
[M+-BF4]. Anal. Calc. for C30H41BF4NOPRu (650.51):
C, 55.39%; H, 6.35%; F, 11.68%; Ru, 15.54%. Found:
C, 55.27%; H, 6.59%; F, 12.03%; Ru, 15.50%. IR
A solution of 100 mg (0.12 mmol) of 3a in 10 ml of
CH2Cl2 was reacted with 6.8 mg (0.12 mmol) of ace-
tonitrile at ambient temperature. The color of the solu-
tion brightens spontaneously to yellow. After 5 min of
(CH2Cl2): w(CN)=2275 (w) cm−1
.
31P{1H} NMR

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E. Lindner et al. / Journal of Organometallic Chemistry 555 (1998) 247–253
(101.25 MHz, CD2Cl2, 22°C): l=36.4 (s). 13C{1H}
NMR (62.90 MHz, CD2Cl2, 22°C): l=133.4–128.9
(m, C–Ph), 124.7 (s, CH3CN), 101.7 (d, J(PC)=2.7
Table 2
Atomic coordinates (×104) of 4a with equivalent isotropic displace-
ment coefficients (A ×103)a
2
˚
2
Hz, C6Me6), 68.6 (s, CH2O), 58.6 (s, OCH3), 28.3 (d,
1J(PC)=26.3 Hz, PCH2), 15.4 (s, C6Me6), 4.4 (s,
CH3CN), −2.2 (d, 2J(PC)=16.2 Hz, RuCH3). 1H-
NMR (250.13 MHz, CD2Cl2, 22°C): l=0.4 (d,
3J(PH)=6.3 Hz, 3H, RuCH3).
Atom
x
y
z
U(eq)
Ru(1)
Cl(1)
P(1)
O(1)
B(1)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
1626(1)
1651(1)
3123(1)
3261(2)
8249(3)
9915(3)
619(1)
−309(1)
988(1)
2362(1)
1621(1)
1763(1)
3672(2)
3773(2)
2957(2)
2853(3)
3452(3)
4160(3)
4267(3)
3662(2)
2365(2)
1735(2)
1764(2)
2428(2)
3058(2)
3045(2)
4924(2)
5519(2)
5779(2)
5438(2)
4833(2)
4547(2)
4106(2)
4216(2)
4061(2)
3781(2)
3668(2)
3836(2)
981(2)
19(1)
31(1)
21(1)
40(1)
25(1)
39(1)
53(1)
61(2)
55(1)
41(1)
32(1)
37(1)
50(1)
45(1)
38(1)
30(1)
28(1)
28(1)
38(1)
42(1)
42(1)
36(1)
26(1)
30(1)
39(1)
41(1)
41(1)
31(1)
26(1)
31(1)
28(1)
36(1)
25(1)
24(1)
25(1)
34(1)
34(1)
23(1)
39(1)
24(1)
24(1)
25(1)
33(1)
34(1)
35(1)
37(1)
40(1)
42(1)
36(1)
35(1)
26(1)
43(1)
40(1)
46(1)
39(1)
27(1)
33(1)
49(1)
101(1)
−2117(2)
−1872(2)
−1645(2)
−1412(2)
−1417(2)
−1654(2)
−1884(2)
−2321(2)
−2696(2)
−3334(2)
−3593(2)
−3221(2)
−2565(2)
−2619(2)
−3039(2)
−3397(2)
−3324(2)
−2913(2)
−2545(2)
−915(2)
−406(2)
−460(2)
−1027(2)
−1532(2)
−1501(2)
579(2)
4.9. tert-Butyl-isocyanide(chloro)(p6-hexamethylbenzene)
[(methoxyethyl)diphenylphosphine-P]ruthenium(II)
tetraphenylborate (6a)
11002(4)
11762(4)
11455(3)
10376(3)
9563(3)
7121(3)
6740(3)
6936(3)
7499(3)
7872(3)
7708(3)
7368(3)
7359(3)
8332(4)
9298(3)
9288(3)
8317(3)
7862(3)
7161(3)
5970(3)
5496(3)
6209(3)
7419(3)
4839(3)
2719(3)
−17(3)
289(2)
Addition of t-BuNC (12.5 mg, 0.15 mmol) to a
solution of 3a (130 mg, 0.15 mmol) in 10 ml of
dichloromethane, followed by 5 min of stirring at room
temperature, gave a yellow solution, which was evapo-
rated to dryness. The residue was washed with 10 ml of
n-hexane, and dried in vacuo yielding 142 mg (100%) of
6a; mp. 56°C (dec); MS (FD, 60°C): m/e 627 [M+-
BPh4]. Anal. Calc. for C56H64BClNOPRu (945.43): C,
71.14%; H, 6.82%; Cl, 3.75%; N, 1.48%; Ru, 10.69%.
Found: C, 70.98%; H, 7.02%; Cl, 3.80%; N, 1.64%; Ru,
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(52)
C(48)
C(45)
C(41)
C(43)
C(50)
C(29)
C(42)
C(28)
C(30)
C(40)
C(36)
C(35)
C(31)
C(27)
C(46)
C(49)
C(34)
C(26)
C(47)
C(44)
C(32)
C(51)
C(33)
O(2)
10.57%. IR (KBr): w(CN)=2162 (vs) cm−1 31P{1H}
.
NMR (101.25 MHz, CD2Cl2, 22°C): l=34.0 (s).
13C{1H} NMR (62.90 MHz, CD2Cl2, 22°C): l=164.5
(q, 1J(CB)=49.4 Hz, ipso-C of BPh4), 142.2 (s,
CNCMe3), 135.9–121.7 (m, C–Ph), 106.9 (s, C6Me6),
67.5 (s, CH2O), 59.5 (s, CNCMe3), 58.0 (s, OCH3), 30.4
1
295(2)
1796(2)
619(2)
1577(2)
773(1)
−250(2)
−78(2)
1365(2)
−442(2)
438(1)
1211(2)
1307(2)
1935(2)
922(2)
−305(2)
1472(2)
544(2)
2163(2)
204(2)
2235(2)
385(2)
1157(2)
248(2)
1780(2)
1497(1)
1625(2)
1482(2)
3155(2)
1181(2)
3172(2)
2550(2)
1805(2)
2423(2)
2021(2)
1851(2)
1890(2)
1565(2)
3213(2)
837(2)
(s, CNCMe3), 30.3 (d, J(PC)=32.1 Hz, PCH2), 15.5
(s, C6Me6).
858(3)
−319(3)
−829(3)
4586(3)
197(3)
4.10. p2-Ethene(p6-hexamethylbenzene)
[(methoxyethyl)diphenylphosphine-P]
(methyl)ruthenium(II) tetrafluoroborate (7b)
5514(3)
4232(3)
880(3)
A solution of 100 mg (0.16 mmol) of 3b in 10 ml of
CH2Cl2 was treated with ethene (1 bar) at room tem-
perature. After 3 h stirring the solvent was removed
under reduced pressure. The residue was washed with
10 ml of n-hexane to give a yellow precipitate which
was collected by filtration (G3) and dried in vacuo
yielding 105 mg (100%) of 7b; mp. 60°C (dec); MS
(FAB, 50°C): m/e 534 [M+-BF4–CH3]. Anal. Calc. for
C30H42BF4OPRu (637.51): C, 56.52%; H, 6.64%; F,
11.92%; Ru, 15.85%. Found: C, 56.27%; H, 6.59%; F,
12.23%; Ru, 15.85%. 31P{1H} NMR (101.25 MHz,
CD2Cl2, 22°C): l=41.0 (s). 13C{1H} NMR (62.90
MHz, CD2Cl2, −30°C): l=135.1–128.5 (m, C–Ph),
110.5 (s, C6Me6), 67.3 (s, CH2O), 58.3 (s, OCH3), 51.5,
2524(3)
2680(3)
1844(3)
6099(3)
1440(3)
−1001(3)
2169(3)
5760(3)
1366(3)
−256(3)
1327(4)
268(3)
643(2)
311(2)
1306(2)
3961(2)
1062(2)
−57(2)
851(2)
2614(2)
2472(2)
−383(2)
3893(2)
−564(2)
3539(1)
2218(2)
2983(2)
4276(2)
1494(4)
4039(2)
4034(3)
4762(3)
4685(4)
C(37)
C(38)
C(39)
1
46.2 (s, C2H4), 22.9 (d, J(PC)=31.0 Hz, PCH2), 15.4
1419(2)
(s, C6Me6), 1.4 (d, 2J(PC)=16.2 Hz, RuCH3). 1H-
NMR (250.13 MHz, CD2Cl2, 22°C): l=0.6 (d,
3J(PH)=6.6 Hz, 3H, RuCH3).
a Equivalent isotropic U defined as one-third of the trace of the
orthogonalized Uij tensor.

E. Lindner et al. / Journal of Organometallic Chemistry 555 (1998) 247–253
253
4.11. Crystallographic analysis
References
[1] J.C. Jeffrey, T.B. Rauchfuss, Inorg. Chem. 18 (1979) 2658.
Single crystals of 4a were obtained by slow diffu-
sion of diethyl ether into a concentrated solution of
4a in CH2Cl2. The crystals were mounted on a glass
fiber and transferred to a P4 Siemens diffractometer,
using graphite-monochromated Mo–Kh radiation. A
rotation photograph was taken and a photo search
was performed to find a suitable reduced cell. The
lattice constants were determined with 25 precisely
centered high-angle reflections and refined by least-
squares methods. The final cell parameters for 4a are
summarized in Table 1. The atomic coordinates and
equivalent isotropic displacement parameters for 4a
are given in Table 2. Intensities were collected with
the ꢀ-scan technique with scan speed varying from
6.5 to 29.3° min−1 in ꢀ. Scan range for 4a was 1.0
and absorption correction was applied (C-scan, maxi-
mum and minimum transmission: 0.693, 0.654). The
structure was solved by Patterson methods [17] and
refined by least squares with anisotropic thermal
parameters for all non-hydrogen atoms (based on F2).
Hydrogen atoms were included in calculated positions
(riding model). Maximum and minimum peaks in the
final difference synthesis were 0.303 and −0.352
[2] (a) A. Bader, E. Lindner, Coord. Chem. Rev. 108 (1991) 27. (b)
E. Lindner, S. Pautz, M. Haustein, Coord. Chem. Rev. 155
(1996) 145.
[3] (a) H. Yang, M. Alvarez-Gressier, N. Lugan, R. Mathieu,
Organometallics 16 (1997) 1401. (b) P. Braunstein, Y. Chauvin,
J. Na¨hring, A. Decian, J. Fischer, A. Tiripicchio, F. Ugozzoli,
Organometallics 15 (1996) 5551. (c) S.J. Chadwell, S.J. Coles,
P.G. Edwards, M.B. Hursthouse, J. Chem. Soc. Dalton Trans.
(1996) 1105. (d) T.B. Higgins, C.A. Mirkin, Inorg. Chim. Acta
240 (1995) 347. (e) T. Braun, P. Steinert, H. Werner, J.
Organomet. Chem. 488 (1995) 169. (f) H. Werner, A. Stark, P.
Steinert, G. Gru¨nwald, J. Wolf, Chem. Ber. 128 (1995) 49.
[4] (a) E. Lindner, M. Haustein, R. Fawzi, M. Steimann, P. Wegner,
Organometallics 13 (1994) 5021. (b) E. Lindner, M. Haustein,
H.A. Mayer, K. Gierling, R. Fawzi, M. Steimann, Organometal-
lics 14 (1995) 2246. (c) E. Lindner, M. Gepra¨gs, K. Gierling, R.
Fawzi, M. Steimann, Inorg. Chem. 34 (1995) 6106. (d) E.
Lindner, S. Pautz, M. Haustein, J. Organomet. Chem. 509 (1996)
215. (e) E. Lindner, B. Keppeler, H.A. Mayer, K. Gierling, R.
Fawzi, M. Steimann, J. Organomet. Chem. 526 (1996) 175. (f) E.
Lindner, B. Keppeler, P. Wegner, Inorg. Chim. Acta 258 (1997)
97. (g) E. Lindner, J. Dettinger, H.A. Mayer, H. Ku¨hbauch, R.
Fawzi, M. Steimann, Chem. Ber. 126 (1993) 1317.
[5] E. Lindner, S. Pautz, R. Fawzi, M. Steimann, Organometallics,
submitted.
[6] H. Werner, H. Kletzin, J. Organomet. Chem. 228 (1982) 289.
[7] P.E. Garrou, Chem. Rev. 81 (1981) 229.
[8] S. Pautz, Thesis, University of Tu¨bingen, 1997.
[9] (a) H. Werner, R. Werner, Chem. Ber. 115 (1982) 3766. (b) H.
Kletzin, H. Werner, J. Organomet. Chem. 291 (1985) 213.
[10] B. Demerseman, C. Renouard, R. Le Lagadec, M. Gonzalez, P.
Crochet, P.H. Dixneuf, J. Organomet. Chem. 471 (1994) 229.
[11] F.B. McCormick, D.D. Cox, W.B. Gleason, Organometallics 12
(1993) 610.
e A−3. Further details of the crystal structure in-
˚
vestigation are available on request from the Fach-
informationszentrum Karlsruhe, Gesellschaft fu¨r wis-
senschaftlich-technische Information mbH, D-76344
Eggenstein-Leopoldshafen, on quoting the depository
number CSD-407707, the names of the authors and
the journal citation.
[12] (a) W. Scho¨niger, Microchim. Acta (1955) 123. (b) W. Scho¨niger,
Microchim. Acta (1956) 869.
[13] A. Dirscherl, F. Erne, Microchim. Acta (1961) 866.
[14] G. Brunisholz, J. Michot, Helv. Chim. Acta 37 (1954) 598.
[15] E. Lindner, A. Bader, H.A. Mayer, Z. Anorg. Allg. Chem.
598/599 (1991) 235.
Acknowledgements
[16] E. Lindner, J. Dettinger, A. Mo¨ckel, Z. Naturforsch. B 46 (1991)
1519.
[17] G.M. Sheldrick, SHELXTL V5.03 program, University of Go¨ttin-
gen, Germany, 1995.
Support of this work by the Fonds der Chemischen
Industrie, Frankfurt/Main, Germany is gratefully ac-
knowledged.
.