Supramolecular chemistry of half-sandwich organometallic building blocks based on RuCl2(p-cymene)Ph2PCH2Y

Article abstract of DOI:10.1016/j.jorganchem.2006.07.036

A new series of neutral organometallic building blocks based on piano-stool ruthenium(II) complexes, RuCl₂(p-cymene)Ph₂PCH₂Y [Y = -NHC₆H₄(2-CO₂H) (2a), -NHC₆H₄(3-CO

Full text of DOI:10.1016/j.jorganchem.2006.07.036

Journal of Organometallic Chemistry 691 (2006) 4829–4842
www.elsevier.com/locate/jorganchem
Supramolecular chemistry of half-sandwich organometallic
building blocks based on RuCl2(p-cymene)Ph2PCH2Y
a
a
a
a,
*
Sandra E. Dann , Sean E. Durran , Mark R.J. Elsegood , Martin B. Smith
,
a
a
b
Paul M. Staniland , Salem Talib , Sophie H. Dale
a
Department of Chemistry, Loughborough University, Loughborough, Leics LE11 3TU, UK
Molecular Profiles Ltd., 8 Orchard Place, Nottingham Business Park, Nottingham NG8 6PX, UK
b
Received 26 June 2006; received in revised form 18 July 2006; accepted 18 July 2006
Available online 10 August 2006
Abstract
A new series of neutral organometallic building blocks based on piano-stool ruthenium(II) complexes, RuCl2(p-cymene)Ph2PCH2Y
[Y = -NHC6H4(2-CO2H) (2a), -NHC6H4(3-CO2H) (2b), -NHC6H3(3-CO2H)(6-OCH3) (2c), -NHC6H4(4-CO2H) (2d), -NHC6H3(2-
CO2H)(4-OH) (2e), -NHC6H3(3-OH)(4-CO2H) (2f), -NHC6H3(2-CO2H)(5-CO2H) (2g) and -OH (2h)], were synthesised in high yields
(>88%) from {RuCl2(p-cymene)}2 and the appropriate phosphines 1a–1h. The new tertiary phosphine 1b was prepared by Mannich con-
densation of NH2C6H4(3-CO2H) with Ph2PCH2OH in MeOH. Solution NMR (31P{1H}, 1H), FT-IR and microanalytical data are in full
agreement with the proposed structures. Single crystal X-ray studies confirm that, in each case, compounds 2a, 2b and 2d–2h have piano-
stool arrangements with typical Ru–P, Ru–Cl and Ru–Ccentroid bond lengths. From our crystallographic studies, factors that influence
the supramolecular assemblies of these ruthenium(II) complexes include: (i) the type of functional group present, (ii) the geometric dis-
position of the –N(H)CH2PPh2, –CO2H and –OH groups around the central benzene scaffold, and (iii) the solvents used in the recrys-
tallisations. Hence in isomers 2a and 2b, molecules are associated into head-to-tail dimer pairs through classical intermolecular O–Hꢀ ꢀ ꢀO
hydrogen bonding. This feature is also observed in isomer 2d but dimer pairs are further associated to give a 1-D chain through assisted
intermolecular N–Hꢀ ꢀ ꢀCl hydrogen bonding. The additional 4-hydroxo group in 2e promotes a ladder arrangement via intermolecular
O–Hꢀ ꢀ ꢀO and O–Hꢀ ꢀ ꢀCl hydrogen bonding. In contrast the isomeric compound 2f does not show head-to-tail O–Hꢀ ꢀ ꢀO hydrogen bond-
ing but instead O–Hꢀ ꢀ ꢀCl and N–Hꢀ ꢀ ꢀO intermolecular hydrogen bonding is observed. Depending on the choice of solvent (MeOH or
DMSO), 2g forms extended networks based on chains (2g Æ DMSO Æ 1.5MeOH) or tapes (2g Æ 3MeOH). In 2h, a single intramolecular O–
Hꢀ ꢀ ꢀCl hydrogen bond is observed for each independent molecule. The X-ray structure of one representative tertiary phosphine, 1f, has
also been determined.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Phosphine ligands; Ruthenium(II); Supramolecular chemistry; Organometallic complexes; X-ray crystallography
1. Introduction
These range from their interesting and varied coordination
chemistry [1–3] including DNA binding studies [4–6] to
applications in areas such as chemosensors/highly selective
receptors [7,8] and catalysis [9–12]. Furthermore these
organometallic fragments have been used in the synthesis
of cyclometallated [13–15] and chiral half-sandwich com-
pounds [16,17]. Metal arenes have also been employed in
the controlled stepwise assembly of organometallic supra-
molecular squares and rectangles [18,19] and, more
There has been considerable interest in the chemistry of
M(arene) (M = Ru, Rh, Ir; arene = g6-p-cymene, g5-Cp*,
etc.) organometallic moieties for a variety of purposes.
*
Corresponding author. Tel.: +44 1509 222553; fax: +44 1509 223925.
E-mail address: m.b.smith@lboro.ac.uk (M.B. Smith).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.07.036

4830
S.E. Dann et al. / Journal of Organometallic Chemistry 691 (2006) 4829–4842
recently, water-soluble heterobimetallic coordination
polymers containing CpRu+ (and AgCl2ꢁ) have been
synthesised by Peruzzini and co-workers [20]. Prior to
our work, and as far as we are aware, the supramolecular
chemistry of mononuclear Ru(arene) organometallic
complexes utilising hydrogen bonding interactions has
not been studied [21]. Other groups have described crystal
engineering studies using metal-arene organometallic
components based on either Cr [22], Mn [23], Fe [24], Co
[24] or Rh [25].
selection of these compounds and reveal that (i) the nature
of the substituent influences the solid state structures, (ii)
the predisposition of functional groups around the central
benzene core is crucial, and (iii) the choice of recrystallising
solvent is important in controlling the hydrogen bonded
supramolecular assemblies of these organometallic
compounds.
2. Experimental
Standard Schlenk techniques were used for the synthesis
of 1b whilst all other reactions were carried out in air using
previously distilled solvents unless otherwise stated. The
ligands 1a and 1c–1h have been reported elsewhere
[32,36] and the metal precursor {RuCl2(p-cymene)}2 pre-
pared according to a known procedure [37]. All other
chemicals were obtained from commercial sources and
used directly without further purification.
η6-arene ligand
can be modified
Ru
Cl
L
Metathesis or
halide abstraction
Cl
Various two electron
ligands (L) can be introduced
I
Infrared spectra were recorded as KBr pellets in the
range 4000–200 cmꢁ1 on a Perkin–Elmer System 2000 Fou-
rier-transform spectrometer, 1H NMR spectra (250 or
400 MHz) on a Bruker AC250 FT spectrometer with chem-
ical shifts (d) in ppm to high frequency of Si(CH3)4 and
coupling constants (J) in Hz, 31P{1H} NMR spectra were
recorded on JEOL FX90Q or Bruker DPX-400 FT spec-
trometers with chemical shifts (d) in ppm to high frequency
of 85% H3PO4. All NMR spectra were measured in CDCl3
unless otherwise stated. Elemental analyses (Perkin–Elmer
2400 CHN Elemental Analyzer) were performed by the
Loughborough University Analytical Service within the
Department of Chemistry.
Our rationale to a standardised study of self-assembly
and supramolecular behaviour within a series of organo-
metallic ruthenium(II) complexes led us to analyse the
key structural features of a piano-stool compound such
as I. Inspection of I reveals three potential routes by which
manipulation of the ligands can be used to influence hydro-
gen bonded supramolecular architectures. Bis sandwich
compounds have been prepared via halide abstraction of
the chloride ligands, using a silver(I) salt such as
CF3SO3Ag, from {RuCl2(p-cymene)}2 or {RuCl(Cp*)}4
in acetone or THF/MeCN and subsequent incorporation
of other arene ligands with H-bonding capabilities [26].
Alternatively arene functionalisation with polar append-
ages (e.g. OH, NH2) suitable for H-bonding have been
described although their synthetic procedures are non-tri-
val [27]. Moreover from X-ray crystallographic studies,
secondary interactions tend to be restricted to intramolec-
ular O–Hꢀ ꢀ ꢀCl [27b] or intermolecular O–Hꢀ ꢀ ꢀCl [27c]
H-bonding. Neutral two-electron donor ligands such as
tertiary phosphines, PR3, are known to readily cleave
Ru–Cl-Ru bridges [28] such as {RuCl2(p-cymene)}2 to give
mononuclear RuCl2(p-cymene)(PR3) complexes. Typically
in these examples all three R substituents on phosphorus
are equivalent and either alkyl or aryl based. We are una-
ware of any systematic studies exploring the supramolecu-
lar chemistry of RuCl2(p-cymene)(PR3) with phosphines
from a similar ligand library. As part of ongoing studies
in our group [29–35] we have used Mannich-based conden-
sation reactions as an excellent procedure for synthesising
highly functionalised tertiary and ditertiary phosphines.
Herein we describe the use of isomeric, carboxylic acid or
mixed phenol/carboxylic acid containing tertiary phos-
phines, Ph2PCH2Y, for the preparation of a range of
RuCl2(p-cymene)(Ph2PCH2Y) complexes. These piano-
stool compounds have been characterised by spectroscopic
2.1. Preparation of 1b
The amine NH2C6H4(3-CO2H) (0.345 g, 2.52 mmol) and
Ph2PCH2OH (0.557 g, 2.58 mmol) was dissolved in MeOH
(HPLC grade, 10 mL) to give a yellow solution. The solu-
tion was stirred at room temperature for 5 h and evapo-
rated to dryness under reduced pressure. Yield: 0.637 g.
31P{1H} NMR spectroscopy confirmed 1b as the major
phosphorus containing species.
2.2. Preparation of 2a–2h
A typical procedure is given here for 2f. To a CH2Cl2
(10 mL) solution of {RuCl2(p-cymene)}2 (0.052 g, 0.085
mmol) was added 1f (0.058 g, 0.17 mmol). The solution
was stirred for 15 mins and the volume concentrated to
ca. 2 mL under reduced pressure. Addition of diethyl ether
(20 mL) gave an orange solid which was collected by suc-
tion filtration and dried in vacuo. Yield: 0.099 g, 88%.
Yields for the other compounds prepared in this study
are given in parentheses: 2a (90%), 2c (96%), 2d (93%), 2e
(99%), 2g (94%) and 2h (92%). Microanalytical data: 2a,
C30H32NO2PRuCl2, requires: C, 56.17; H, 5.02; N, 2.18.
Found: C, 56.11; H, 5.06; N, 3.35%. 2b, C30H32NO2PRu-
Cl2 Æ Et2O Æ H2O, requires: C, 55.66; H, 6.06; N, 1.91.
1
(31P{1H}, H NMR) and analytical methods. Furthermore
single crystal X-ray structures have been determined for a

Table 1
Details of the X-ray data collections and refinements for compounds 1f, 2a, 2b Æ OEt2 Æ H2O, 2d–2f, 2g Æ 3MeOH, 2g Æ DMSO Æ 1.5MeOH and 2h
Compound
Formula
1f
2a
2b Æ OEt2 Æ H2O
2d
2e
2f
2g Æ 3MeOH
2g0DMSO Æ
1.5MeOH
2h
C20H18NO3P
C30H32Cl2-
NO2PRu
641.51
0.31 · 0.13 ·
0.10
C34H44Cl2-
NO4PRu
733.64
0.32 · 0.30 ·
0.24
C30H32Cl2-
NO2PRu
641.51
0.31 · 0.27 ·
0.07
C30H32Cl2-
NO3PRu
657.51
0.17 · 0.14 ·
0.06
C30H32Cl2-
NO3PRu
657.51
0.32 · 0.22 ·
0.09
C34H44Cl2-
NO7PRu
781.64
0.13 · 0.10 ·
0.06
C34.50H44Cl2-
NO6.50PRu
811.71
0.30 · 0.08 ·
0.05
C23H27Cl2OPRu
Molecular weight
Crystal dimensions
351.32
0.39 · 0.27 ·
0.07
522.39
0.30 · 0.23 · 0.12
Crystal morphology
and colour
Crystal system
Space group
Plate and
colourless
Triclinic
Block and
orange
Monoclinic
P21/c
13.5846(6)
15.8035(7)
13.8433(6)
Block and red
Plate and
orange
Monoclinic
P21/c
20.7870(8)
14.2415(6)
20.8011(8)
Block and
orange
Triclinic
Plate and
orange
Triclinic
Block and
red
Monoclinic
P21/n
12.8635(11)
23.909(2)
13.0686(11)
Needle and
orange
Monoclinic
P21/c
13.6073(6)
23.6146(10)
22.6565(10)
Block and orange
Monoclinic
P21/n
10.0428(5)
13.0085(6)
25.7188(12)
Monoclinic
P21/c
21.8690(11)
7.4956(4)
27.2257(14)
ꢀ
ꢀ
ꢀ
P1
P1
P1
˚
a (A)
7.6267(9)
9.8428(12)
11.9688(14)
93.937(2)
97.013(2)
96.175(2)
883.53(18)
2
7.3541(4)
11.7103(6)
17.0938(9)
101.894(2)
91.946(2)
100.604(2)
1411.93(13)
2
7.6332(3)
12.7330(6)
14.5975(7)
93.591(2)
97.100(2)
91.725(2)
1404.11(11)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
102.964(2)
90.368(2)
107.088(2)
118.077(2)
91.936(2)
97.296(2)
3
˚
V (A )
2896.2(2)
4
0.809
3359.9(3)
4
0.711
5886.1(4)
8
0.796
3546.2(5)
4
0.685
7276.1(5)
8
0.725
4426.7(4)
8
1.034
Z
l (mmꢁ1
)
0.174
0.834
0.839
h Range (ꢁ)
2.59–28.76
7845
4090
1.98–29.06
25427
7051
1.58–29.00
29239
8147
1.76–29.02
51475
14272
9734
1.81–29.15
12716
6571
1.60–29.05
12588
6524
1.70–29.11
31307
8627
1.72–25.00
52812
12806
7463
2.25–28.04
36919
10115
7237
Measured reflections
Independent reflections
Observed reflections
(F2 > 2r(F2))
3212
5734
6315
5425
5695
4755
Rint
0.0173
0.0429
0.1171
0.648, ꢁ0.290
0.0227
0.0278
0.0626
0.454, ꢁ0.359
0.0357
0.0374
0.0869
1.082, ꢁ0.678
0.0443
0.0422
0.1112
1.756, ꢁ0.759
0.0219
0.0305
0.0628
0.615, ꢁ0.773
0.0148
0.0277
0.0686
0.965, ꢁ0.320
0.1021
0.0531
0.1381
0.802, ꢁ1.162
0.0724
0.0504
0.1444
1.168, ꢁ0.839
0.0354
0.0355
0.0804
0.901, ꢁ0.699
R [F2 > 2r(F2)]a
wR2 (all data)b
Largest difference map
3
˚
features (e A )
P
P
a
R = iFoj ꢁ jFci/ jFoj.
P
P
2
2
1=2
b
wR2 ¼ f ½wðF 2o ꢁ F c2Þ ꢂ= ½wðF 2oÞ ꢂg
.

4832
S.E. Dann et al. / Journal of Organometallic Chemistry 691 (2006) 4829–4842
Found: C, 54.98; H, 5.89; N, 2.07%. 2c, C31H34NO3-
PRuCl2, requires: C, 55.44; H, 5.11; N, 2.09. Found: C,
55.06; H, 4.91; N, 1.82%. 2d, C30H32NO2PRuCl2 Æ
0.5CH2Cl2, requires: C, 53.55; H, 4.87; N, 2.05. Found:
C, 53.94; H, 5.18; N, 1.95%. 2e, C30H32NO3PRuCl2,
requires: C, 54.80; H, 4.92; N, 2.13. Found: C, 54.28; H,
4.75; N, 2.25%. 2f, C30H32NO3PRuCl2 Æ 0.5CH2Cl2,
requires: C, 52.32; H, 4.76; N, 2.00. Found: C, 52.48; H,
4.37; N, 1.32%. 2g, C31H32NO4PRuCl2, requires: C,
54.31; H, 4.71; N, 2.04. Found: C, 53.44; H, 4.66; N,
1.90%. 2h, C23H27OPRuCl2, requires: C, 52.87; H, 5.22.
Found: C, 52.62; H, 5.15%. The powder diffraction pat-
terns for 2a and 2f fit with those calculated from single
crystal data.
2.3. X-ray crystallography
Suitable crystals of 1f were obtained upon slow evapora-
tion to dryness of a CDCl3 solution. The compounds 2a, 2d
and 2h were obtained by vapour diffusion of Et2O into
either a CDCl3 or CDCl3/MeOH solution over several
days, respectively. Compound 2b was obtained by evapora-
tion of a CH2Cl2/Et2O filtrate to dryness over several days.
Suitable crystals of 2e and 2f were obtained by vapour dif-
fusion of Et2O into CDCl3/MeOH solutions. For 2g
vapour diffusion of Et2O into either CDCl3/MeOH/DMSO
or CDCl3/MeOH solutions gave crystals suitable for single
crystal X-ray crystallography. All measurements were
made on a Bruker AXS SMART 1000 CCD area-detector
diffractometer, at 150 K, using graphite-monochromated
˚
Mo Ka radiation (k = 0.71073 A) and narrow frame expo-
sures (0.3ꢁ) in x. Cell parameters were refined from the
observed (x) angles of all strong reflections in each data
set. Intensities were corrected semiempirically for absorp-
tion based on symmetry-equivalent and repeated reflec-
tions. The structures were solved by direct methods and
refined on F2 values for all unique data by full-matrix
least-squares. Table 1 gives further details. All non-hydro-
gen atoms were refined anisotropically. CH hydrogen
atoms were placed in calculated positions (C–H 0.98–
˚
1.00 A) and refined using a riding model. NH hydrogen
atoms were located in a difference Fourier map and refined
freely in all cases except compound 2g, where restraints
were applied to the N–H bond length. OH hydrogen atoms
were placed in calculated positions and refined using a
riding model in all cases except compounds 2f and 2h,
where restraints were applied to the O–H bond length.
Water hydrogen atoms in 2b were located in a difference
Fourier map and refined freely. Uiso(H) values were fixed
at 1.2Ueq(N,Caromatic,Cmethine,Cmethylene) and 1.5Ueq(O,
C
methyl) in all cases except compound 2e, where Uiso(NH)
values were freely refined. Compounds 2g Æ 3MeOH,
2g Æ DMSO Æ 1.5MeOH and 2h were refined using disorder
models. In 2g Æ 3MeOH, two molecules of MeOH were dis-
ordered [major refined occupancy = 80.0(7)%] and OH
hydrogen atoms were placed on the major component of
the disorder model only. In 2g Æ DMSO Æ 1.5MeOH, one

S.E. Dann et al. / Journal of Organometallic Chemistry 691 (2006) 4829–4842
4833
DMSO molecule was modelled with two alternative posi-
tions for the S atom [major refined occupancy = 93.9(4)%].
The two MeOH molecules were modelled with C atoms
disordered over two positions [major refined occupan-
cies = 52.7(18) and 83.6(17)%], however, no H atoms could
be located. In 2h, the complex containing Ru(2) was mod-
elled with two alternative positions for the Ru, Cl and P
atoms and the p-cymene ligand [major refined occu-
pancy = 76.3(3)%]. In compounds 2g Æ 3MeOH, 2g Æ DM-
SO Æ 1.5MeOH and 2h, restraints were applied to the
geometry of the disordered groups and the anisotropic
displacement parameters of some atoms. Programs used
were Bruker AXS SMART and SAINT for diffractometer con-
trol and frame integration [38], Bruker SHELXTL for struc-
ture solution and refinement [39], Diamond for molecular
graphics [40], and local programs. In the following figures,
anisotropic displacement ellipsoids are drawn at the 50%
probability level. Hydrogen bonds are shown as thin,
dashed black lines; the g6-coordination mode of the
p-cymene ligand is shown using a thick, dashed grey line
between the ruthenium ion and the centroid of the
aromatic ring.
shown some of these ligands serve as convenient building
blocks for the preparation of linear, dinuclear gold(I)
complexes [35] with unusual finite and infinite structures.
In order to further understand the supramolecular capa-
bility of these ligands we turned our attention to
half-sandwich organometallic compounds based on
ruthenium(II).
Reaction of NH2C6H4(3-CO2H) and Ph2PCH2OH in a
1:1 molar ratio, in MeOH at ambient temperature, gave
Ph2PCH2NHC6H4(3-CO2H) (1b) in addition to small
amounts (ca. 20%) of the disubstituted phosphine
(Ph2PCH2)2NC6H4(3-CO2H) (Eq. (1)). Both phosphines
could readily be distinguished by their characteristic 31P
NMR resonances (Table 2) which differ by ca. 10 ppm
between both phosphorus species. No attempts were made
to purify 1b which was used directly in the complexation
studies.
CO2H
CO2H
CO2H
Ph2PCH2OH
MeOH
PPh2
PPh2
+
NH
N
PPh2
NH2
1b
Powder X-ray diffraction data were recorded on a Bru-
ker D8 powder diffractometer using monochromated cop-
per radiation over the 2h range 5–60ꢁ using a 0.0147ꢁ 2h
step. Simulated powder data were generated from the cif
files of the single crystal structures using the program
ATOMS v5.0.1 for comparison with the experimental
patterns.
ð1Þ
The ruthenium(II) complexes RuCl2(p-cymene)Ph2-
PCH2Y [Y = -NHC6H4(2-CO2H) (2a), -NHC6H4(3-CO2H)
(2b), -NHC6H3(3-CO2H)(6-OCH3) (2c), -NHC6H4(4-
CO2H) (2d), -NHC6H3(2-CO2H)(4-OH) (2e), -NHC6H3-
(3-OH)(4-CO2H) (2f), -NHC6H3(2-CO2H)(5-CO2H) (2g)
and -OH (2h)] were prepared by standard bridge cleavage
of {RuCl2(p-cymene)}2 [37] with two equivalents of 1a–1h
in dichloromethane at room temperature. The 31P{1H}
NMR data are in good agreement with P-monodentate
coordination as inferred by the downfield shift (typically
ca. 20 ppm) of their 31P resonances (Table 2). Further sup-
3. Results and discussion
3.1. Synthesis and characterisation
We have previously found that Mannich based con-
densation reactions are extremely facile for the syntheses
of functionalised tertiary and ditertiary phosphines
[29–34]. Carboxylic acid phosphines [32,34] can be
prepared by this procedure and furthermore, we have
1
porting evidence is seen in the H NMR spectra showing
well resolved signals for the p-cymene and PCH2– [d(H)
4.34–4.72 ppm] groups. Other characterising data are given
in Section 2 and Table 2.
Fig. 1. View of a hydrogen bonded dimer of 1f. Selected bond lengths and angles for 1f: P(1)–C(1) 1.8515(18), P(1)–C(9) 1.8254(19), P(1)–C(15)
˚
1.8324(18), C(1)–N(1) 1.454(2), C(8)–O(1) 1.249, C(8)–O(2) 1.320(2) A. C(1)–P(1)–C(9) 103.73(9), C(1)–P(1)–C(15) 97.70(8), C(9)–P(1)–C(15) 100.70(8),
0
P(1)–C(1)–N(1) 112.45(12)ꢁ. Symmetry codes: ꢁx ꢁ 1, ꢁy, ꢁz ꢁ 1.

Table 3
Selected bond distances (A) and bond angles (ꢁ) for compounds 2a, 2b Æ OEt2 Æ H2O, 2d–2f, 2g Æ 3MeOH, 2g Æ DMSO Æ 1.5MeOH and 2h
˚
2a
2b Æ OEt2 Æ H2O
2d
2e
2f
2g Æ 3MeOH
2g Æ DMSO Æ 1.5MeOH
2ha
˚
Bond length (A)
Ru(1)–P(1)
Ru(1)–Cl(1)
Ru(1)–Cl(2)
2.3292(5)
2.4166(5)
2.4233(5)
1.695
2.3443(7)
2.4222(7)
2.4249(7)
1.701
2.3616(10) [2.3423(10)]
2.4166(9) [2.4357(10)]
2.4079(9) [2.4176(10)]
1.693 [1.699]
2.3347(6)
2.4202(6)
2.4362(6)
1.706
2.3439(6)
2.4278(5)
2.4169(5)
1.705
2.3515(13)
2.4125(12)
2.4319(12)
1.699
2.3486(18) [2.3346(17)]
2.4167(16) [2.4246(16)]
2.4060(17) [2.4338(18)]
1.694 [1.696]
2.3516(8)
2.4279(8)
2.4171(8)
1.710
b
Ru(1)–Carene
P(1)–C(11)
C(11)–N(1)
C–O(1)
C–O(2)
C–O(3)
1.8590(19)
1.444(2)
1.322(2)
1.241(2)
1.880(3)
1.440(3)
1.312(3)
1.235(4)
1.851(4) [1.848(3)]
1.452(5) [1.450(5)]
1.305(5) [1.310(5)]
1.243(5) [1.250(5)]
1.859(2)
1.442(3)
1.320(3)
1.239(3)
1.878(2)
1.432(3)
1.334(3)
1.230(3)
1.859(5)
1.450(6)
1.319(7)
1.223(7)
1.324(6)
1.204(7)
1.859(7) [1.860(7)]
1.441(8) [1.436(8)]
1.320(8) [1.318(8)]
1.214(8) [1.228(8)]
1.299(9) [1.326(10)]
1.224(9) [1.196(10)]
1.856(3)
1.414(5)
C–O(4)
Bond angle (ꢁ)
Cl(1)–Ru(1)–P(1)
Cl(2)–Ru(1)–P(1)
Cl(1)–Ru(1)–Cl(2)
Ru(1)–P(1)–C(11)
P(1)–C(11)–N(1)
P(1)–C(1)–O(1)
a
85.450(18)
84.386(18)
88.725(18)
112.41(6)
86.12(2)
82.94(2)
88.47(2)
113.17(8)
116.70(18)
87.24(3) [87.03(3)]
84.66(3) [84.36(3)]
88.93(3) [88.26(3)]
112.74(12) [111.55(12)]
117.4(3) [116.8(2)]
85.77(2)
85.11(2)
86.76(2)
114.67(7)
112.62(15)
87.133(19)
82.823(19)
86.816(19)
113.60(7)
87.58(5)
85.04(5)
86.01(4)
114.84(16)
113.7(3)
87.43(6) [86.99(6)]
84.71(6) [84.25(6)]
85.89(6) [87.52(6)]
115.3(2) [114.2(2)]
114.3(4) [114.0(4)]
85.22(3)
87.72(3)
87.03(3)
115.30(12)
114.49(13)
117.82(16)
112.8(3)
Data given here for the non-disordered molecule only.
Ruꢀ ꢀ ꢀarene distance is taken between the ruthenium(II) ion and the least-squares plane of the aromatic ring of the g6-p-cymene ligand.
b

S.E. Dann et al. / Journal of Organometallic Chemistry 691 (2006) 4829–4842
4835
0
influences secondary hydrogen bonding interactions we ini-
tially focussed on varying the site of the carboxylic acid
group (2-, 3- or 4-position) with respect to the diph-
enylphosphino moiety. Hence in 2a (Fig. 2), we find that
molecules are linked into head-to-tail dimer pairs [R22ð8Þ
graph set motif] through intermolecular O–Hꢀ ꢀ ꢀO hydro-
codes: 2 ꢁ x, 1 ꢁ y, 1 ꢁ z]. However, this time due to
the remote proximity of the NH group with respect to
the carboxylic acid group, no intramolecular N–Hꢀ ꢀ ꢀ O
hydrogen bonding is observed [43]. Instead the NH group
is involved in hydrogen bonding to a water solvate
˚
˚
[N(1)ꢀ ꢀ ꢀO(4) 2.999(3) A, Hꢀ ꢀ ꢀO 2.16(3) A; N–Hꢀ ꢀ ꢀO
176(3)ꢁ]. Hydrogen bonding is also observed between the
water and Et2O solvent molecules [O(4)ꢀ ꢀ ꢀO(3)
0
˚
˚
gen bonding [O(1)ꢀ ꢀ ꢀO(2 ) 2.641(2) A, Hꢀ ꢀ ꢀO 1.80 A;
0
O–Hꢀ ꢀ ꢀO 176.4ꢁ; symmetry codes: ꢁx, 1 ꢁ y, 1 ꢁ z]. Fur-
˚
˚
thermore, the close proximity of the secondary amine
group enables additional intramolecular N–Hꢀ ꢀ ꢀO hydro-
gen bonding with the carbonyl oxygen atom of the carbox-
2.757(4) A, Hꢀ ꢀ ꢀO 1.71(5) A; O–Hꢀ ꢀ ꢀO 165(4)ꢁ].
Even when the carboxylic acid group is located at the 4-
position a similar motif is found for 2d (Fig. 4) where again
the strong propensity for head-to-tail dimer pair formation
is observed for each unique molecule [O(1)ꢀ ꢀ ꢀO(20)
˚
˚
ylic acid group [N(1)ꢀ ꢀ ꢀO(2) 2.645(2) A, Hꢀ ꢀ ꢀO 1.98(2) A;
N–Hꢀ ꢀ ꢀO 140(2)ꢁ] [43].
˚
˚
The 3-substituted isomer 2b has been structurally char-
acterised as 2b Æ Et2O Æ H2O upon crystallisation from a
CH2Cl2/Et2O solution (Fig. 3). As observed with 2a, 2b dis-
plays a similar dimer pair association through intermolec-
2.643(4) A, Hꢀ ꢀ ꢀO 1.81 A; O–Hꢀ ꢀ ꢀO 173.1ꢁ for molecule
1; O(3)ꢀ ꢀ ꢀO(400) 2.615(4) A, Hꢀ ꢀ ꢀO 1.78 A; O–Hꢀ ꢀ ꢀO
˚ ˚
0
175.7ꢁ for molecule 2; symmetry codes: ꢁx, 2 ꢁ y, ꢁz;
00
x, 1.5 ꢁ y, 0.5 + z]. Utilising the NH group these pairs
ular
O–Hꢀ ꢀ ꢀO
hydrogen
bonding
[O(1)ꢀ ꢀ ꢀO(20)
associate into 12-membered rings [graph set R22ð12Þ] via
˚
˚
2.624(3) A, Hꢀ ꢀ ꢀO 1.79 A; O–Hꢀ ꢀ ꢀO 175.3ꢁ; symmetry
intermolecular N–Hꢀ ꢀ ꢀCl hydrogen bonding [N(1)ꢀ ꢀ ꢀCl(300)
0
Fig. 2. Views of the (a) molecular and (b) dimeric structures of 2a. Only the OH and NH hydrogen atoms are shown in (b). Symmetry codes: ꢁx, 1 ꢁ y,
1 ꢁ z.

4836
S.E. Dann et al. / Journal of Organometallic Chemistry 691 (2006) 4829–4842
Fig. 3. Views of the (a) molecular and (b) dimeric structure of 2b Æ Et2O Æ H2O. Only the OH and NH H-atoms are shown. The H2O and Et2O solvent
0
molecules are only shown in (b). Symmetry codes: 2 ꢁ x, 1 ꢁ y, 1 ꢁ z.
˚
˚
3.389(3) A, Hꢀ ꢀ ꢀCl 2.74(4) A; N–Hꢀ ꢀ ꢀCl 142(4)ꢁ for mole-
secondary amine) still gives rise to a head-to-tail motif rem-
000
0
˚
˚
˚
cule 1; N(2)ꢀ ꢀ ꢀCl(2 ) 3.232(3) A, Hꢀ ꢀ ꢀCl 2.53(4) A; N–
Hꢀ ꢀ ꢀCl 146(4)ꢁ for molecule 2; symmetry codes: 000x,
1.5 ꢁ y, z ꢁ 0.5] giving rise to 1-D chain motifs.
iniscent of that seen in 2a [O(2)ꢀ ꢀ ꢀO(1 ) 2.647(2) A, Hꢀ ꢀ ꢀO
˚
1.84(3) A; O–Hꢀ ꢀ ꢀO 173(3)ꢁ]. The observation of an intra-
˚
molecular H-bond [N(1)ꢀ ꢀ ꢀO(1) 2.677(3) A, Hꢀ ꢀ ꢀO
˚
In summary, the formation of head-to-tail dimer pairs
through O–Hꢀ ꢀ ꢀO intermolecular H-bonding is observed
regardless of the position (2-, 3- or 4-) of the CO2H group
on the tertiary phosphine. These findings reflect the strong
desire for hydrogen bonding between neighbouring carbox-
ylic acid groups giving rise to this frequently encountered
supramolecular synthon [41,44]. Not surprisingly we also
find when the CO2H group is distanced from the secondary
amine, intermolecular N–Hꢀ ꢀ ꢀCl H-bonding (as in 2d) is
preferred over intramolecular N–Hꢀ ꢀ ꢀO H-bonding (for
2a).
2.04(3) A; N–Hꢀ ꢀ ꢀO 138(2)ꢁ] may play some role in ‘‘lock-
ing’’ the -N(H)-arene group into a fixed conformation. In
this way the phenolic group gives rise to an overall chain
structure that results from intermolecular O–Hꢀ ꢀ ꢀCl hydro-
gen bonding involving this group and a terminal Ru–Cl
00
˚
˚
ligand [O(3)ꢀ ꢀ ꢀCl(2 ) 3.2049(19) A, Hꢀ ꢀ ꢀCl 2.43(3) A; O–
Hꢀ ꢀ ꢀCl 172(3)ꢁ] (Fig. 5). The net effect here is the formation
of larger 30-membered hydrogen bonded rings [graph set
motif R46ð30Þ] in comparison to the 12-membered rings
found in 2d.
In the isomeric complex 2f in which the -OH and -CO2H
groups are predisposed in 3- and 4-positions, respectively,
relative to the –NH group, we see a completely new pack-
ing arrangement. The major feature, in stark contrast with
2e and the uncoordinated ligand 1f, is the absence of a clas-
sic head-to-tail dimer pair. Instead molecules are linked
into side-by-side arrangements through intermolecular
Having established the role of the carboxylic acid group
predisposition we next sought to consider what effect the
introduction of additional polar groups to the -N(H)-phe-
nyl backbone may have on the supramolecular chemistry
through alternate hydrogen bonding patterns. In 2e, reten-
tion of the 2-positioned -CO2H group (with respect to the

S.E. Dann et al. / Journal of Organometallic Chemistry 691 (2006) 4829–4842
4837
Fig. 4. Views of the (a) molecular structure and (b) extended hydrogen bonded structure of 2d. Only the OH and NH hydrogen atoms are shown and
0
00
unsubstituted Ph rings have been removed for clarity in (b). Symmetry codes: ꢁx, 2 ꢁ y, ꢁz; x, 1.5 ꢁ y, 0.5 + z.
0
˚
˚
N–Hꢀ ꢀ ꢀO [N(1)ꢀ ꢀ ꢀO(3 ) 3.251(3) A, Hꢀ ꢀ ꢀO 2.32(3) A, N–
2e. The solvate 2g Æ 3MeOH was crystallised via the vapour
diffusion of Et2O into a CDCl3/MeOH solution of 2g. There
are no direct hydrogen bonds between molecules of 2g in
2g Æ 3MeOH, instead the molecules are linked by MeOH
molecules into tapes propagating in the crystallographic
[ꢁ1 0 1] direction. The MeOH molecules are essentially
inserted into (carboxylic acid)O–Hꢀ ꢀ ꢀCl hydrogen bonds,
leading to two hydrogen bonding motifs. In the first motif,
00
˚
Hꢀ ꢀ ꢀO 166(2)ꢁ] and O–Hꢀ ꢀ ꢀCl [O(2)ꢀ ꢀ ꢀCl(1 ) 3.026(2) A,
˚
Hꢀ ꢀ ꢀCl 2.06(4) A, O–Hꢀ ꢀ ꢀCl 162(3)ꢁ] hydrogen bonding.
This leads to alternate 12- and 24-membered rings afford-
ing a tape arrangement. The adjacent phenolic OH group
is used in forming an intramolecular O–Hꢀ ꢀ ꢀO hydrogen
˚
˚
bond [O(3)ꢀ ꢀ ꢀO(1) 2.615(3) A, Hꢀ ꢀ ꢀO 1.90(3) A, O–Hꢀ ꢀ ꢀO
131(3)ꢁ] with the carbonyl oxygen atom of the carboxylic
acid group (Fig. 6).
one MeOH molecule has been inserted giving
a
˚
We next looked at the function played by polar solvents
on H-bonding arrangements. Compound 2g was crystal-
lised from two related solvent systems, affording the two
solvates 2g Æ 3MeOH and 2g Æ DMSO Æ 1.5MeOH. The
molecular structure of 2g is shown in Fig. 7a. In both sol-
vates, the NH group is involved in an intramolecular hydro-
gen bond with the carbonyl group of the adjacent
CO2Hꢀ ꢀ ꢀMeOHꢀ ꢀ ꢀCl sequence [O(2)ꢀ ꢀ ꢀO(5) 2.663(6) A,
0
˚ ˚
Hꢀ ꢀ ꢀO 1.83 A, O–Hꢀ ꢀ ꢀO 172ꢁ; O(5)ꢀ ꢀ ꢀCl(2 ) 3.133(4) A,
0
˚
Hꢀ ꢀ ꢀCl 2.30 A, O–Hꢀ ꢀ ꢀCl 169ꢁ, symmetry codes: x + 0.5,
0.5 ꢁ y, z ꢁ 0.5]. In the second motif, two MeOH molecules
have been inserted giving a CO2Hꢀ ꢀ ꢀMeOHꢀ ꢀ ꢀMeOHꢀ ꢀ ꢀCl
˚
˚
sequence [O(4)ꢀ ꢀ ꢀO(6) 2.616(8) A, Hꢀ ꢀ ꢀO 1.78 A, O–Hꢀ ꢀ ꢀO
˚
˚
178ꢁ; O(6)ꢀ ꢀ ꢀO(7) 2.666(9) A, Hꢀ ꢀ ꢀO 1.91 A, O–Hꢀ ꢀ ꢀO
00
˚
˚
carboxylic acid group [2g Æ 3MeOH Nꢀ ꢀ ꢀO 2.656(6) A,
149ꢁ; O(7)ꢀ ꢀ ꢀCl(1 ) 3.138(5), Hꢀ ꢀ ꢀCl 2.31 A, O–Hꢀ ꢀ ꢀCl
167ꢁ, symmetry codes: 00 x ꢁ 0.5, 0.5 ꢁ y, z + 0.5] (Fig. 7b).
The solvate 2g Æ DMSO Æ 1.5MeOH was crystallised
from the vapour diffusion of Et2O into a CDCl3/MeOH/
˚
Hꢀ ꢀ ꢀO 1.95(4) A, N–Hꢀ ꢀ ꢀO 135(4)ꢁ; 2g Æ DMSO Æ 1.5MeOH
˚
˚
Nꢀ ꢀ ꢀO 2.647(7)/2.630(7) A, Hꢀ ꢀ ꢀO 1.94/1.92 A, N–Hꢀ ꢀ ꢀO
136/137ꢁ]. This feature resembles that found with 2a and

4838
S.E. Dann et al. / Journal of Organometallic Chemistry 691 (2006) 4829–4842
Fig. 5. Views of the (a) molecular structure and (b) extended hydrogen bonded structure of 2e. Only the O–H and N–H 0h0 ydrogen atoms are shown and
0
000
unsubstituted Ph rings and p-cymene ligands have been removed for clarity in (b). Symmetry codes: 1 ꢁ x, 1 ꢁ y, ꢁz; x, y + 1, z; x, y ꢁ 1, z.
DMSO solution of 2g. As observed in 2g Æ 3MeOH, there
are no hydrogen bonds between the two unique half-sand-
wich complexes in 2g Æ DMSO Æ 1.5MeOH; both unique
complexes are involved in different hydrogen bonding pat-
terns. Each complex has one CO2H group hydrogen
bonded to a DMSO molecule through the combination
of a strong O–Hꢀ ꢀ ꢀO and a weaker C–Hꢀ ꢀ ꢀO hydrogen
bond using a methyl CH group of the DMSO molecule
forming a R22ð7Þ graph set motif [molecule containing
complex, with the choice of CO2H group leading to the
existence of two hydrogen bonding patterns. In one com-
plex/DMSO adduct, the CO2H group involved is adjacent
to the NH group, while in the second complex/DMSO
adduct, the CO2H group involved is positioned further
from the NH group.
The CO2H groups lacking interactions with DMSO
form hydrogen bonds to MeOH molecules, resulting in
˚
CO2Hꢀ ꢀ ꢀMeOHꢀ ꢀ ꢀCl [O(3)ꢀ ꢀ ꢀO(13) 2.748(13) A, Hꢀ ꢀ ꢀO
˚
˚
˚
˚
Ru(1): O(1)ꢀ ꢀ ꢀO(10) 2.589(7) A, Hꢀ ꢀ ꢀO 1.76 A, O–Hꢀ ꢀ ꢀO
1.91 A, O–Hꢀ ꢀ ꢀO 173ꢁ; O(12)ꢀ ꢀ ꢀCl(1) 00 3.061(8) A;
00
˚
˚
˚
170ꢁ; C(66)ꢀ ꢀ ꢀO(2) 3.191(9) A, Hꢀ ꢀ ꢀO 2.34 A, C–Hꢀ ꢀ ꢀO
O(13)ꢀ ꢀ ꢀO(12 ) 2.654(15) A, symmetry codes: x, 1.5 ꢁ y,
z + 0.5] and CO2Hꢀ ꢀ ꢀMeOHꢀ ꢀ ꢀMeOHꢀ ꢀ ꢀCl motifs
˚
144ꢁ; molecule containing Ru(2): O(5)ꢀ ꢀ ꢀO(9) 2.596(8) A,
˚
˚
˚
˚
Hꢀ ꢀ ꢀO 1.80 A, O–Hꢀ ꢀ ꢀO 158ꢁ; C(64)ꢀ ꢀ ꢀO(6) 3.434(10) A,
[O(7)ꢀ ꢀ ꢀO(11) 2.711(9) A, Hꢀ ꢀ ꢀO 1.91 A, O–Hꢀ ꢀ ꢀO 159ꢁ;
0 0
˚
˚
Hꢀ ꢀ ꢀO 2.58 A, C–Hꢀ ꢀ ꢀO 146ꢁ]. The DMSO molecules
O(11)ꢀ ꢀ ꢀCl(4 ) 3.270(6) A, symmetry codes: x, 1.5 ꢁ y,
z ꢁ 0.5], as observed in 2g Æ 3MeOH. Two unique sets of
hydrogen bond to one of the two CO2H groups in each

S.E. Dann et al. / Journal of Organometallic Chemistry 691 (2006) 4829–4842
4839
Fig. 6. Views of the (a) molecular structure and (b) extended hydrogen bonded structure of 2f. Only the O–H and N–H hydrogen atoms are shown;
0
00
unsubstituted Ph rings have been removed for clarity in (b). Symmetry codes: ꢁx ꢁ 1, 1 ꢁ y, ꢁz; ꢁx ꢁ 1, 2 ꢁ y, ꢁz.
chains are formed, both propagating parallel to the crystal-
lographic c axis. It is clear from a comparison of Fig. 7b
and Fig. 8a and b that the DMSO molecules have inserted
into the hydrogen bonding motifs observed in 2g Æ 3MeOH,
disrupting the tape structure of 2g Æ 3MeOH to create zig-
zag chains.
In order to demonstrate the importance of the –CO2H
and –OH groups attached to the -N(H)-arene backbone
we also determined the X-ray structure of 2h (Fig. 9). In
each independent molecule there is only one intramolecular
˚
O–Hꢀ ꢀ ꢀCl hydrogen bond [O(1)ꢀ ꢀ ꢀCl(1) 3.102(3) A, Hꢀ ꢀ ꢀCl
˚
2.274(18) A; O–Hꢀ ꢀ ꢀCl 165(5)ꢁ for molecule 1; O(2)ꢀ ꢀ ꢀCl(4)

4840
S.E. Dann et al. / Journal of Organometallic Chemistry 691 (2006) 4829–4842
Fig. 7. Views of the (a) molecular structure and (b) extended hydrogen bonded structure of 2g Æ 3MeOH. Only the OH and NH hydrogen atoms are shown
0
and unsubstituted Ph rings have been removed for clarity in (b). The MeOH solvent molecules are not shown in (a). Symmetry codes: x + 0.5, 0.5 ꢁ y,
00
z ꢁ 0.5; x ꢁ 0.5, 0.5 ꢁ y, z + 0.5.
˚
˚
3.151(4) A, Hꢀ ꢀ ꢀCl 2.35(2) A; O–Hꢀ ꢀ ꢀCl 160(5)ꢁ for mole-
cule 2]. This observation is similar to that previously
reported by Therrien and co-workers who noted a similar
intramolecular O–Hꢀ ꢀ ꢀCl hydrogen bond in the ruthe-
patterns of 2a and 2f are in excellent agreement with
the simulated powder patterns that were derived from
their single crystal X-ray structures. This implies the
hydrogen bonding arrangements hypothesised in the sin-
gle crystal determination are present in the bulk unrecrys-
tallised material and have not been directed by the solvent
used for single crystal growth. However, in the powder
pattern of 2e, additional reflections are exhibited that
are extraneous to those presented in the theoretical
pattern indicating that the bulk unrecrystallised sample
is probably a mixture of phases. Finally, the powder
diffraction data collected from the bulk 2d unrecrystallised
sample is in poor agreement with the theoretical pattern
generated from the single crystal study implying the
possible presence of some impurities and/or the solvent
nium(II)
complex
RuCl2{g6-C6H5(CH2)3OH}(PPh3)
[27b]. Hence while the functionalisation of the tertiary
phosphine/arene ligands has, in effect, been reversed the
propensity for this type of secondary interaction is evident
here.
3.3. Powder X-ray diffraction studies
We have also performed some preliminary powder
X-ray diffraction studies with four representative exam-
ples namely 2a, 2d, 2e and 2f. The experimental powder

S.E. Dann et al. / Journal of Organometallic Chemistry 691 (2006) 4829–4842
4841
Fig. 8. Views of the extended hydrogen bonded structure of 2g Æ DMSO Æ 1.5MeOH, showing two unique chains formed by (a) molecules containing Ru(1)
and (b) molecules 0containing Ru(2). Only the OH, NH and methyl hydrogen atoms are shown and unsubstituted Ph rings have been removed for clarity.
00
Symmetry codes: x, 1.5 ꢁ y, z ꢁ 0.5; x, 1.5 ꢁ y, z + 0.5.
4. Conclusions
Our studies with organometallic half-sandwich ruthe-
nium(II) complexes containing highly functionalised
monodentate tertiary phosphines has revealed that a vari-
ety of self-assembled structures can be achieved. The pre-
dominant manner by which these supramolecular
architectures can be controlled utilises the type and posi-
tion of the functional group(s) on the tertiary phosphine.
Furthermore, the choice of highly polar recrystallisation
solvents such as MeOH/DMSO disrupts any strong O–
Hꢀ ꢀ ꢀO H-bonding between carboxylic acid groups in
favour of extended structures that incorporate DMSO
and/or MeOH molecules. Further systematic studies of
these isomeric ligands towards other metal centres are in
Fig. 9. View of the molecular structure of 2h showing only one of the two
independent molecules.
progress and will be reported in due course.
Acknowledgements
used for single crystal growth has had a structure direct-
ing affect and coordinated to the moieties during
crystallisation.
We are grateful to Johnson-Matthey for the kind dona-
tion of RuCl3 Æ xH2O and the EPSRC Mass Spectrometry

4842
S.E. Dann et al. / Journal of Organometallic Chemistry 691 (2006) 4829–4842
[17] C. Ganter, Chem. Soc. Rev. 32 (2003) 130.
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Ed. Engl. 37 (1998) 1694.
Service centre at Swansea. We also thank the Leverhulme
Trust (S.T.) and EPSRC (S.E.D., P.M.S.) for funding.
[19] Y. Yamamoto, H. Suzuki, N. Tajima, K. Tatsumi, Chem. Eur. J. 8
(2002) 372.
Appendix A. Supplementary material
[20] C. Lidrissi, A. Romerosa, M. Saoud, M. Serrano-Ruiz, L. Gonsalvi,
M. Peruzzini, Angew. Chem., Int. Ed. 44 (2005) 2568.
[21] L. Brammer, Chem. Soc. Rev. 33 (2004) 476.
[22] (a) L. Brammer, J.C. Mareque Rivas, R. Atencio, S. Fang, F.C.
Pigge, J. Chem. Soc., Dalton Trans. (2000) 3855;
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(1999) 461.
[23] M. Oh, G.B. Carpenter, D.A. Sweigart, Acc. Chem. Res. 37 (2004) 1.
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[25] S.U. Son, J.A. Reingold, G.B. Carpenter, D.A. Sweigart, Chem.
Commun. (2006) 708.
A complete set of X-ray crystallographic structural data
for compounds 1f, 2a, 2b Æ Et2O Æ H2O, 2d–2f, 2g Æ 3MeOH,
2g Æ DMSO Æ 1.5MeOH and 2h (CCDC Nos. 295350–
295358, respectively) is available at the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK (fax: +44 1223 336 033; e-mail: depos-
it@ccdc.cam.ac.uk) on request, quoting the deposition
numbers. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.jorganchem.2006.07.036.
[26] (a) A. Schluter, K. Bieber, W.S. Sheldrick, Inorg. Chim. Acta 340
¨
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(b) D. Vichard, M. Gruselle, H. El Amouri, G. Jaouen, J. Vaisser-
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