Synthesis and structure of a chelating arene-ruthenium complex [RuCl2(PPh2(CH2)3-η 6-C6H5)]

Article abstract of DOI:10.1016/S0022-328X(97)00750-X

The synthesis of an arene-phosphine ligand, Ph₂P(CH₂)₃Ph, has provided a route into a new chelating arene-phosphine-ruthenium complex, [RuCl₂(PPh₂(CH₂)₃-η ⁶-C₆H₅)] which has been structurally characterized. This complex can be made by thermolysis of [(η⁶-MeC₆H₄CHMe₂)RuCl ₂(PPh₂(CH₂)₃Ph)] or electrochemically utilizing the formation of the labile seventeen-electron ruthenium(III) species [(η⁶-MeC₆H₄CHMe₂)RuCl ₂(PPh₂(CH₂)₃Ph)]⁺ which can be converted in good yield into [RuCl₂(PPh₂(CH₂)₃-η ⁶-C₆H₅)].

Full text of DOI:10.1016/S0022-328X(97)00750-X

Journal of Organometallic Chemistry 559 (1998) 141–147
Synthesis and structure of a chelating arene–ruthenium complex
[RuCl2(PPh2(CH2)3-p6-C6H5)]
Paul D. Smith a, Anthony H. Wright b,*
a Department of Chemistry, Uni6ersity of Otago, P.O. Box 56, Dunedin, New Zealand
b Department of Chemistry and Biochemistry, Massey Uni6ersity, Pri6ate Bag 11222, Palmerston North, New Zealand
Received 8 November 1997
Abstract
The synthesis of an arene–phosphine ligand, Ph2P(CH2)3Ph, has provided a route into a new chelating arene–phosphine–ruthe-
nium complex, [RuCl2(PPh2(CH2)3-p6-C6H5)] which has been structurally characterized. This complex can be made by thermolysis
of [(p6-MeC6H4CHMe2)RuCl2(PPh2(CH2)3Ph)] or electrochemically utilizing the formation of the labile seventeen-electron
ruthenium(III) species [(p6-MeC6H4CHMe2)RuCl2(PPh2(CH2)3Ph)]+ which can be converted in good yield into
[RuCl2(PPh2(CH2)3-p6-C6H5)]. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Ruthenium; Arene–phosphine; Electrochemistry
1. Introduction
This reaction has been well documented for related
complexes [3] but the complete loss of the ligand
may be an unwanted side reaction. This report de-
scribes the results of an investigation into the possibility
of increasing the robustness of these complexes towards
arene substitution. An obvious way of stabilizing the
arene–metal interaction is to ‘tie’ the arene group onto
another ligand and hence capitalize on the chelate
effect.
The chemistry of arene–ruthenium complexes is rich
and varied as a result of the strong arene–metal bond
and the availability of reactive arene-containing com-
pounds [1]. The complexes are finding increasing appli-
cation in organic synthesis and catalysis, as catalysts, or
catalyst precursors [2]. One of the critical reactions in
such applications may involve progressive removal of
the arene ligand from p6 to p4, p2, and possibly involv-
ing complete loss of the arene ligand.
* Corresponding author.
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(97)00750-X

142
P.D. Smith, A.H. Wright / Journal of Organometallic Chemistry 559 (1998) 141–147
Table 1
Atomic co-ordinates (×10−4) and equivalent isotropic displacement
parameters (A ×10−3) for (3)
˚
x
y
z
U(eq)
Ru(1)
P(1)
Cl(1)
Cl(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
6060(1)
6467(1)
8289(1)
5026(2)
8449(2)
5591(6)
7016(6)
6935(7)
5503(8)
4174(7)
4238(6)
8493(7)
9231(6)
9916(6)
7397(6)
5732(8)
5074(10)
6128(9)
7781(9)
8437(7)
9417(6)
8553(7)
9349(9)
6315(1)
7425(1)
7250(1)
5737(1)
6425(3)
5757(3)
5033(3)
4944(3)
5597(4)
6371(4)
5820(4)
6738(4)
7003(4)
8518(3)
8749(4)
9595(5)
10 211(4)
9990(4)
9137(4)
7840(3)
8403(4)
8762(5)
8567(5)
8007(5)
7636(4)
29(1)
32(1)
55(1)
42(1)
42(1)
36(1)
42(1)
50(1)
47(1)
46(1)
47(1)
47(1)
44(1)
38(1)
69(2)
91(3)
72(2)
62(2)
52(1)
38(1)
50(1)
65(2)
71(2)
68(2)
50(1)
5587(1)
4075(2)
3651(1)
8794(6)
8535(5)
7667(6)
7164(6)
7400(6)
8174(6)
9139(6)
8645(6)
6697(7)
6367(6)
6820(10)
7318(13)
7382(9)
6945(8)
6418(7)
3392(6)
2340(7)
692(8)
Examples of chelated cyclic polyene complexes have
been previously reported for ruthenium, such as the
cyclopentadiene derivative [RuCl(PPh3)(PPh2(CH2)2-
p5C5H4)] [4] and further analogues include compounds
containing a p6-arene ring linked to a sulphur atom [5].
For the purpose of this study we have examined adap-
tation of phosphine ligands, since they provide readily
available starting materials and form robust ruthe-
nium–arene complexes under mild conditions [6].
2. Results and discussion
2.1. Synthesis
The preparation of PPh2(CH2)3Ph (1) involved the
cleavage of a phenyl ring from triphenylphosphine with
lithium in THF giving a convenient source of the
reactive lithium diphenylphosphide salt [7,8]. Selective
protonation of the phenyllithium, produced simulta-
neously, was carried out by the addition of an equimo-
lar amount of t-butylchloride to the reaction mixture
[8]. (1) was formed, in 80% yield, by the reaction of this
solution with an equivalent of 1-bromo-3-
phenylpropane.
71(8)
1098(8)
2762(7)
11 037(10)
11 887(8)
11 123(7)
U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor.
The new ligand (1) was introduced to the co-ordina-
tion sphere of the ruthenium by careful addition of two
equivalents of the phosphine to the dimer [(p6-cymene)
RuCl2]2 producing the complex [(p6-MeC6H4CHMe2)
RuCl2(PPh2(CH2)3Ph)] (2).
PhCH CH CH BrPh2PCH2CH2CH2Ph
2
2
“
2
Li,THF
PPh3 “ Li[PPh2]
Thermal arene substitution was explored and reason-
able yields of the complex [RuCl2(PPh2(CH2)3(p6-
C6H5)] (3) could be made by extended heating at 130°C
in refluxing chlorobenzene. After 18 h the resulting
brown product could be purified by chromatography to
give a 50% yield of (3) as orange-red crystals Scheme 1.
2.2. Crystal structure of [RuCl2(PPh2(CH2)3-p6-C6H5)]
(3) (Table 1 and Table 2)
Crystals suitable for an X-ray crystal analysis were
prepared by evaporation from CH2Cl2-EtOH. The
structure of the compound, shown in Fig. 1, is a
pseudo-octahedral arene–ruthenium(II) complex.
The most noticeable feature of the structure is that
the co-ordinated ring is pushed across the face of the
metal so that free end of the ring is significantly lifted
away from the ruthenium. The two carbon atoms in-
Scheme 1. Reaction conditions: (i) Ph2P(CH2)3Ph, CH2C12; (ii) PhCl,
130°C, 18 h; (iii) Pt gauze working electrode, CH2C12-[NBun4][PF6]
(0.1 mol dm−3), +1.5 V[0.0 V (vs SCE), 298 K, N2 (iv) Pt gauze
working electrode, MeCN-[NH4][PF6] (0.1 mol dm−3), +1.5 V[0.0
V (vs SCE), 298 K, N2.
˚
volved, C(5) and C(6) are 2.241(4) and 2.246(5) A from
the ruthenium respectively compared with the other
metal carbon distances which lie in the conventional
˚
2.17–2.20 A range. This distortion probably originates

P.D. Smith, A.H. Wright / Journal of Organometallic Chemistry 559 (1998) 141–147
143
ing a C(7)–C(8)–C(9) angle of 113.6° slightly larger
than the ideal 109.5° for an sp3 carbon.
from the steric constraints imposed by the link between
the ring and the phosphorus atom and the trans influ-
ence of the phosphorus ligand.
1
Solution H and 13C NMR spectra provided struc-
tural information for solutions of (3). The asymmetry
of the link between the co-ordinated ring and the
phosphorus atom, revealed in the X-ray crystal struc-
ture, lowers the symmetry of the molecule from the
ideal C2. However the H spectrum of the co-ordinated
ring contains three signals attributed to the coupling
An examination of the link between the co-ordinated
ring and the phosphorus atom shows that the geometry
about the carbon atoms involved, C(7), C(8) and C(9)
is close to that expected for tetrahedral carbon and the
stereochemistry is such that both the C(7)–C(8) and
C(8)–C(9) adopt gauche conformations.
However the distortion in the structure is a signal
that the control of the strain in the link between the
ring and the phosphorus could be used to tune the
p6–p4 shift of the ring and hence access to a vacant site
on the metal.
The effect of the trans phosphorus ligands has been
reported in related complexes lacking the link between
ring and phosphorus, including [(p6-C6H6)RuCl(dippe)]
[BPh4] [6] and [(p6-arene)RuCl2(PPh2Me)] [9] com-
plexes. The Ru–Cl, Ru–P distances and the P–Ru–C1
angles in (3) are comparable to these analogues.
As would be expected for an octahedral geometry,
three C–C bonds of the coordinated ring lie above the
other three ligands. This results in a barely significant
bond alternation around the ring. Interruption of con-
jugation in this way has been shown to be due to
electronic effects within the molecule, rather than be-
cause of any crystallographic imposed symmetry effects
[10]. The carbon atom C(7), linking the chelating arm
to the p6-C6H5 ring, was essentially in the same plane as
the arene carbons C(1) and C(6). The angle subtended
by these methylene groups suggests some strain, show-
1
between para, meta and ortho positions giving two
3
triplets and one doublet (vicinal coupling, JHH=3 Hz)
of relative intensities 1:2:2, respectively. This apparent
symmetry of the environment of the co-ordinated ring
is likely to be due to the rapid twisting of the co-ordi-
nated ring relative to the rest of the complex. The
spectrum contains two peaks arising from the methyle-
nes, which are accidentally coincident, forming a large
multiplet.
2.3. Electrochemistry
Although the chemistry of arene–ruthenium com-
plexes in the (II) and (O) oxidation states is very well
developed, other possible higher oxidation states are
less well explored. Paramagnetic organometallics are
relatively uncommon but potentially important because
of the higher kinetic lability that can be anticipated
compared with their 18-electron counterparts. Accelera-
tion of arene substitution in 17-electron half sandwich
complexes is well established for chromium [11]. There
are only a few isolated examples of organometallic
complexes of ruthenium(III) known, most based on the
pentamethylcyclopentadienyl (Cp*) ligand [12].
The arene ligand is particularly suitable for forming
paramagnetic compounds because the ligand only mar-
ginally stabilizes metal non-bonding d electrons by
back-bonding to the arene, especially when the metal is
in a positive oxidation state. This is reflected in the
facile removal of electrons from arene clusters such as
[Ru4H4(p6-C6H6)4]2+ [13].
Electrochemical cyclovoltammetric studies have re-
vealed quasi-reversible one-electron Ru(II)–Ru(III) re-
dox behaviour associated a number of mononuclear
arene–ruthenium species, such as the nido-carborane
complex [(p6-C6H6)Ru(Et2C2B4H4)] [14] and a range of
carbene [15], phosphine [16] and isocyanide [17]
derivatives.
An electrochemical investigation of (2) revealed a
quasi-reversible one-electron Ru(II)–Ru(III) redox cou-
ple in CH2Cl2 (E1/2= +1.25 V vs SCE, DE=90 mV,
ipa:ipc=0.91), as illustrated in Fig. 2.
The reversibility of this redox process is solvent
dependent and the addition of MeCN to the cell altered
the nature of the observed Ru(II)–Ru(III) couple. Fig.
3 shows the cyclic voltammogram recorded during a
multiscan experiment, where the initial redox couple
Fig. 1. ORTEP drawing of [RuCl2(PPh2(CH2)3-p6-C6H5)] (3) with 50%
probability thermal ellipsoids.

144
P.D. Smith, A.H. Wright / Journal of Organometallic Chemistry 559 (1998) 141–147
MeCN has no noticeable effect on the process, indi-
cated that the chelating ring is no longer as easily
substituted.
3. Experimental
All syntheses were carried out under a dry nitrogen
atmosphere using conventional Schlenk techniques. Sol-
vents were distilled from appropriate drying agents
prior to use and were deoxygenated immediately before
use. [{(p-cymene)RuCl2}2] was prepared by the litera-
ture method [18]. NMR spectra were recorded on a
Bruker 250 MHz spectrometer.
3.1. 3-Phenylpropyldiphenylphosphine (1)
A suspension of triphenylphosphine (26.2 g, 0.1 mol)
and strips of lithium metal (1.75 g, 0.25 mol) in dry
THF (200 ml), was stirred rapidly for 1 h at 0°C under
an atmosphere of dinitrogen. The solution became deep
red and was allowed to reach room temperature whilst
stirring for a further 30 min. The solution was then
transferred to a clean dry flask away from any excess
Fig. 2. Cyclic voltammogram recorded at a Pt bead working electrode
(vs SCE) for [(p6-MeC6H4CHMe2)RuCl2(PPh2(CH2)3Ph)] (2) (ca. 1
mmol dm−3) in CH2Cl2/[NBu4n][PF6] (0.1 mol dm−3) at 298 K, scan
rate=100 mV s−1 (ferrocene was used an internal calibrant and ip
obeyed a linear relationship with the square root of the scan rate).
was irreversible and a new redox process emerged at a
lower potential (E1/2= +0.56 V vs SCE).
Controlled potential bulk electrolysis of (2) in
MeCN, in which an exhaustive oxidation at +1.5 V
was followed by subsequent reduction at 0.0 V, yielded
a yellow product (Scheme 2). From NMR data the
material isolated was identified as [(MeCN)3RuCl2
(PPh2(CH2)3Ph)] (4) resulting from arene substitution
by MeCN via a kinetically labile Ru(III) intermediate,
consistent with a typical electrochemical–chemical (EC)
process. Attempts to synthesize (4) via thermal or pho-
tochemical methods have failed resulting in either de-
composition or recovery of (2). This emphasizes the
enhanced lability of the Ru(III) species compared with
related Ru(II) complexes.
In the absence of MeCN, the controlled potential
oxidation–reduction process provides an alternative
route to the chelate [RuCl2(PPh2(CH2)3-p6-C6H5)] (3)
leading to isolation of (3) in 75% yield. This method
improves the synthetic route to the chelate complex.
Cyclovoltammetry of (3) shows a similar electro-
chemical behaviour to (2) (E1/2= +1.34 V vs SCE,
DE=80 mV, ipa:ipc=0.94) but in this case addition of
Fig. 3. Cyclovoltammogram of the first (a) and second (b) cycles
recorded for [(p6-MeC6H4CHMe2)RuCl2(PPh2(CH2)3Ph)] (2) upon
addition of 2 ml of MeCN during a multiscan experiment where the
potential was held at +1.5 V for 15 s during each sweep.

P.D. Smith, A.H. Wright / Journal of Organometallic Chemistry 559 (1998) 141–147
145
Scheme 2. The ECE mechanism proposed for the electrochemical preparation of [(MeCN)3RuCl2(PPh2(CH2)3Ph)] (4).
1
lithium metal. A solution of t-butyl chloride (9.3 g,
11.05 ml, 0.1 mol) in THF (50 ml) was added dropwise
with rapid stirring and cooling. The exothermic reac-
tion was accompanied by gas evolution and partial
discharge of colour. The reaction mixture was refluxed
for 15 min and then cooled to room temperature. A
solution of 1-bromo-3-phenylpropane (19.9 g, 14.7 ml,
0.1 mol) in THF (50 ml) was added dropwise with
cooling and rapid stirring. The resulting yellow solution
was refluxed for 30 min and then the solvent was
removed under reduced pressure. The reaction mixture
was purified by column chromatography on alumina
using a mixture of dichloromethane-hexane as eluent.
On removal of the solvent the phosphine was obtained
as a colourless oil which slowly crystallized from cold
diisopropyl ether to yield white crystals of Ph2P
(CH2)3Ph yield 24.3 g, 80%. Anal. Found: C, 82.74; H,
7.14. C21H21P requires C, 82.87; H, 6.95%. NMR
(CDCl3, 250 MHz, 298 K): H, l 7.9–6.9 (m, 15H, Ph),
5.3–5.0 (dd, 4H, MeC6H4CHMe2), 2.62 (t, 2H,
Ph2PCH2CH2CH2Ph), 2.51 (sept, 1H, MeC6H4CH-
Me2), 2.43 (t, 2H, Ph2PCH2 CH2CH2Ph), 1.87 (s, 3H,
MeC6H4CHMe2), 1.32 (m, 2H, Ph2PCH2CH2CH2Ph),
0.73 (d, 6H, MeC6H4CHMe2); 13C, l 141.8–126.91
(Ph), 97.98, 93.7, 90.46, 85.39 (MeC6H4CHMe2), 36.92
(Ph2PCH2CH2CH2Ph), 29.87 (MeC6H4CHMe2), 25.52,
1
25.13, JCP=34 Hz (Ph2PCH2CH2CH2Ph), 22.83 (Ph2
PCH2CH2CH2Ph), 21.05 (MeC6H4CHMe2), 17 (MeC6
H4CHMe2); 31P{1H}, l −117.08.
3.3. [RuCl2(PPh2(CH2)3-p6-C6H5)] (3)
(i) Thermolysis:
A
solution of [(p6-MeC6H4
CHMe2)RuCl2(PPh2(CH2)3Ph)] (305 mg, 0.5 mmol) in
chlorobenzene (20 ml) was heated to 130°C for 18 h.
The solvent was removed from the reaction mixture
and the brown product purified by chromatography on
alumina using dichloromethane as eluent. Recrystalliza-
tion from dichloromethane–ethanol gave orange-red
crystals. Yield 120 mg, 50%. Anal. Found: C, 52.79; H,
4.41. C21H21Cl2PRu requires C, 52.95; H, 4.44%. NMR
1
(CDCl3, 250 MHz, 298 K): H, l 7.5–7.0 (m, 15H, Ph),
2.75 (t, 2H, Ph2PCH2CH2CH2Ph), 2.01 (t, 2H, Ph2
PCH2CH2CH2Ph), 1.78 (quin, 2H, Ph2PCH2CH2CH2
Ph); 13C, l 141.82–125.62 (Ph), 37.98 (Ph2PCH2CH2
CH2Ph), 27.82, 27.46, 1JCP=31 Hz (Ph2PCH2CH2
CH2Ph), 26.73 (Ph2PCH2CH2CH2Ph); 31P{1H}, l −
157 1.
1
(CDCl3, 250 MHz, 298 K): H, l 7.63–7.31 (m, 10H,
Ph), 6.39 (t, 1H, para p6-C6H5), 5.77 (t, 2H, meta p6-
C6H5), 5.16 (d, 2H, ortho p6-C6H5), 2.57 (m, 4H,
Ph2PCH2CH2CH2-p6-C6H5), 2.18 (m, 2H, Ph2PCH2
CH2CH2-p6-C6H5); 13C, l 134.39–128.02 (Ph), 101.2
(para p6-C6H5), 90.3 (meta p6-C6H5), 89.17 (ipso p6-
C6H5), 84.67 (ortho p6-C6H5), 30.79 (Ph2PCH2CH2
CH2-p6-C6H5), 23.17. 22.67, 1JCP=43 Hz (Ph2PCH2
CH2CH2-p6-C6H5), 20.45 (Ph2PCH2CH2CH2-p6-C6H5);
31P{1H}, l −117.45.
3.2. [(p6-MeC6H4CHMe2)RuCl2(PPh2(CH2)3Ph)] (2)
PPh2(CH2)3Ph (669 mg, 2.2 mmol) was added to a
solution of [{(p-cymene)RuCl2}2] (612 mg, 1 mmol) in
50 ml of dichloromethane. The mixture was stirred for
1 h and the product crystallized from a mixture of
dichloromethanediisopropyl ether. Recrystallization
from the same solvent combination gave [(p6-
MeC6H4CHMe2)RuCl2(PPh2(CH2)3Ph)] as red crystals.
Yield 1.01 g, 83%. Anal. Found: C, 61.24; H, 5.91.
C31H35Cl2PRu requires C, 60.98; H, 5.78%. NMR
(ii)
Electrolysis:
A
solution
of
[(p6-
MeC6H4CHMe2)RuCl2(PPh2(CH2)3Ph)] (305 mg, 0.5
mmol) in dichloromethane (15 ml) containing
[NBun4][PF6] (0.1 M) was electrolyzed at +1.5 V (vs

146
P.D. Smith, A.H. Wright / Journal of Organometallic Chemistry 559 (1998) 141–147
(ii)
Electrolysis:
A
solution
of
[(p6-
Table 2
˚
Selected bond lengths [A] and angles [°] for 3
MeC6H4CHMe2)RuCl2(PPh2(CH2)3Ph)] (305 mg, 0.5
mmol) in dichloromethane (15 ml) containing
[NBun4][PF6] (0.1 M) was electrolyzed at +1.5 V (vs
SCE), using a two compartment bulk-electrolysis cell
separated by Vycor porous glass with platinum gauze
working and secondary electrodes, under a dinitrogen
atmosphere at 298 K. The current fell exponentially
during exhaustive-electrolysis (3 h) producing a brown-
red solution. The potential was switched to 0.0 V (vs
SCE) and the solution electrolyzed (1.5 h) forming a
orange-red colour. This solution was removed from the
cell and taken to dryness, washed with ethanol–
methanol, 50:50, (3×50 ml) to remove supporting elec-
trolyte and orange-red crystals were obtained as in
Section 3.3(i). Yield 178 mg, 75%.
Intramolecular distances
Ru(1)–C(6)
Ru(1)–C(3)
Ru(1)–C(1)
Ru(1)–C(2)
Ru(1)–C(4)
Ru(1)–C(5)
Ru(1)–P(1)
Ru(1)–Cl(2)
Ru(1)–Cl(1)
P(1)–C(20)
P(1)–C(9)
P(1)–C(10)
C(1)–C(6)
C(1)–C(2)
C(2)–C(3)
C(2)–C(7)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
C(7)–C(8)
C(8)–C(9)
2.172(5)
2.171(4)
2.180(5)
2.199(4)
2.241(4)
2.246(5)
2.3187(13)
2.4039(14)
2.4271(14)
1.823(5)
1.833(5)
1.838(4)
1.389(7)
1.441(7)
1.411(6)
1.483(7)
1.410(8)
1.370(8)
1.424(7)
1.520(7)
1.536(7)
3.4. [(MeCN)3RuCl2(PPh2(CH2)3Ph)] (4)
A
solution of [(p6-MeC6H4CHMe2)RuCl2(PPh2
(CH2)3Ph)] (305 mg, 0.5 mmol) in acetonitrile (15 ml)
containing [NH4][PF6] (0.1 M) was electrolyzed at +
1.5 V (vs SCE) as in Section 3.3(ii) producing a brown-
red solution. A subsequent electrolysis at 0.0 V (vs
SCE) was carried out yielding a yellow solution, which
was removed from the cell and take to dryness and the
resulting yellow solid was washed with water (3×50
ml), to remove supporting electrolyte, and dried under
vacuum. NMR (CD3CN, 250 MHz, 298 K) 1H, l
7.56–7.01 (m, 15H, Ph), 2.61 (m, 2H, Ph2PCH2C-
H2CH2Ph), 2.48 (m, 2H, Ph2PCH2CH2CH2Ph), 2.06
(m, 2H Ph2PCH2CH2CH2Ph), 1.57 (s, 9H, (MeCN)3
RuCl2); 13C, l 142.73–126.88 (Ph), 125.14 ((MeCN)3
RuCl2), 37.4 (Ph2PCH2CH2CH2Ph), 26.49, 26.19,
1JCP=25 Hz (Ph2PCH2CH2CH2Ph), 26.01 (Ph2PCH2
CH2CH2Ph), 3.92 ((MeCN)3RuCl2); 31P{1H}, l −
93.68.
Intramolecular angles
P(1)–Ru(1)–Cl(2)
P(1)–Ru(1)–Cl(1)
Cl(2)–Ru(1)–Cl(1)
C(9)–P(1)–Ru(1)
C(2)–C(7)–C(8)
C(7)–C(8)–C(9)
C(8)–C(9)–P(1)
84.26(5)
90.67(5)
88.79(6)
110.0(2)
116.4(4)
113.4(4)
113.2(3)
structure was solved using the program SHELXS86 [19]
and refined with SHELXL93 [20] Fig. 1. was drawn with
ORTEP3 [21]. Important bond lengths and angles are
given in Table 2. The hydrogens were included in
calculated positions and refined as riding atoms.
4. Supplementary Material
3.5. Crystal data and structure determination for (3)
C21H21Cl2PRu, M=476.33, triclinic, space group P1( ,
Tables of crystallographic data, including atomic co-
ordinates and anisotropic thermal parameters, inter-
atomic distances and angles and listings of calculated
and observed structure factors are available. Ordering
information is given on any masthead page.
˚
a=8.192(3), b=8.43(3), c=14.871(5) A, h=82.05(3)°,
3
˚
i=79.76(3)°, k=73.68(2)°, V=965.6 A , Z=2, Dc=
1.64 g cm−3, v(Mo−Kh)=1.172 mm−1, F(000)=
480, data were collected for 3360 reflections of which
3131 with I\3|(I) were considered observed, R=
0.043, wR2=0.134.
References
Cell dimensions and their standard deviations were
obtained by least squares refinement of diffractometer
setting angles for 12 centred reflections close to 13° in
q. Intensities of 3360 independent reflections (2°BqB
25°) were measured on a Hilger and Watts Y290 dif-
fractometer in a ꢀ-2q scan mode.
The structure analysis used 3131 reflections with IB
3|(I) after correction for Lorentz and polarization
factors. No corrections were made for absorption. The
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