Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes

Article abstract of DOI:10.1039/b808798a

Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me₃SiCCC₆F₅ and RuCl(dppe)Cp′ [Cp′ = Cp, Cp*] in the presence of KF in MeOH give the monoruthenium complexes Ru(CCC₆F₅)(dppe)Cp′ [Cp′ = Cp (2); Cp* (3)], which are related to the known compound Ru(CCC₆F ₅)(PPh₃)₂Cp (1). Treatment of Me ₃SiCCC₆F₅ with Pt₂(μ-dppm) ₂Cl₂ in the presence of NaOMe in MeOH gave the bis(alkynyl) complex Pt₂(μ-dppm)₂(CCC₆F ₅)₂ (4). The Pd(0)/Cu(i)-catalysed reactions between Au(CCC₆F₅)(PPh₃) and Mo(≡CBr)(CO) ₂Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)borate], Co₃(μ₃-CBr)(μ-dppm)(CO)₇ or ICCFc [Fc = (η⁵-C₅H₄)FeCp] afford Mo(≡CCCC ₆F₅)(CO)₂Tp* (5), Co₃(μ ₃-CCCC₆F₅)(μ-dppm)(CO)₇ (6) and FcCCCCC₆F₅ (7), respectively. The diruthenium complexes 1,4-{Cp′(PP)RuCC}₂C₆F₄ [(PP)Cp′ = (PPh₃)₂Cp (8); (dppe)Cp (9); (dppe)Cp* (10)] are prepared from 1,4-(Me₃SiCC)₂C₆F₄ in a manner similar to that described for the monoruthenium complexes 1-3. The non-fluorinated complexes 1,4-{Cp′(PP)RuCC}₂C₆H ₄ [(PP)Cp′ = (PPh₃)₂Cp (11); (dppe)Cp (12); (dppe)Cp* (13)], prepared for comparison, are obtained from 1,4-(Me₃SiCC)₂C₆H₄. Spectro-electrochemical studies of the ruthenium aryl and arylene alkynyl complexes 2-3 and 8-13, together with DFT-based computational studies on suitable model systems, indicate that perfluorination of the aromatic ring has little effect on the electronic structures of these compounds, and that the frontier orbitals have appreciable diethynylphenylene character. Molecular structure determinations are reported for the fluoroaromatic complexes 1, 2, 3, 6 and 10.

Full text of DOI:10.1039/b808798a

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PAPER
www.rsc.org/dalton | Dalton Transactions
Some transition metal complexes derived from mono- and
di-ethynyl perfluorobenzenes†
David J. Armitt,a Michael I. Bruce,*a Maryka Gaudio,a Natasha N. Zaitseva,a Brian W. Skelton,b
Allan H. White,b Boris Le Guennic,c,d Jean-Franc¸ois Halet,c Mark A. Fox,e Rachel L. Roberts,e
Frantisˇek Hartl‡ f and Paul J. Low*e
Received 23rd May 2008, Accepted 21st August 2008
First published as an Advance Article on the web 17th October 2008
DOI: 10.1039/b808798a
Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from
trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation
∫
reaction sequences. Reactions between Me3SiC CC6F5 and RuCl(dppe)Cp¢ [Cp¢ = Cp, Cp*] in the
∫
presence of KF in MeOH give the monoruthenium complexes Ru(C CC6F5)(dppe)Cp¢ [Cp¢ = Cp (2);
∫
Cp* (3)], which are related to the known compound Ru(C CC6F5)(PPh3)2Cp (1). Treatment of
∫
Me3SiC CC6F5 with Pt2(m-dppm)2Cl2 in the presence of NaOMe in MeOH gave the bis(alkynyl)
∫
complex Pt2(m-dppm)2(C CC6F5)2 (4). The Pd(0)/Cu(I)-catalysed reactions between
∫
Au(C CC6F5)(PPh3) and Mo(∫CBr)(CO)2Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)borate],
5
∫
∫
Co3(m3-CBr)(m-dppm)(CO)7 or IC CFc [Fc = (h -C5H4)FeCp] afford Mo(∫CC CC6F5)(CO)2Tp* (5),
∫
∫
∫
Co3(m3-CC CC6F5)(m-dppm)(CO)7 (6) and FcC CC CC6F5 (7), respectively. The diruthenium
∫
∫
complexes 1,4-{Cp¢(PP)RuC C}2C6F4 [(PP)Cp¢ = (PPh3)2Cp (8); (dppe)Cp (9); (dppe)Cp* (10)] are
prepared from 1,4-(Me3SiC C)2C6F4 in a manner similar to that described for the monoruthenium
∫
complexes 1–3. The non-fluorinated complexes 1,4-{Cp¢(PP)RuC C}2C6H4 [(PP)Cp¢ = (PPh3)2Cp (11);
∫
(dppe)Cp (12); (dppe)Cp* (13)], prepared for comparison, are obtained from 1,4-(Me3SiC C)2C6H4.
Spectro-electrochemical studies of the ruthenium aryl and arylene alkynyl complexes 2–3 and 8–13,
together with DFT-based computational studies on suitable model systems, indicate that
perfluorination of the aromatic ring has little effect on the electronic structures of these compounds,
and that the frontier orbitals have appreciable diethynylphenylene character. Molecular structure
determinations are reported for the fluoroaromatic complexes 1, 2, 3, 6 and 10.
the occupied frontier orbitals or destabilisation of the unoccupied
Introduction
frontier orbitals. Our interest in organometallic fluorine chem-
istry stems from early work concerning the displacement of an
Substitution of ring hydrogens by fluorines in aromatic com-
pounds results in dramatic differences in properties,1 such as the
marked increase in acidity of C6F5CO2H when compared with
benzoic acid (Ka = 4.2 ¥ 10-4 vs. 6.2 ¥ 10-5),2 and the tendency
of the polyfluoroaromatics to undergo nucleophilic substitution.3
In addition, the introduction of strongly electron-withdrawing
fluorine atoms at strategic points in a molecular structure might be
expected to fine-tune electronic properties through stabilisation of
aromatic F atom by carbonylmetal anions.4 Later, the synthesis
5
∫
of the s-alkynyl complex Ru(C CC6F5)(PPh3)2Cp (1) from the
corresponding chloride and pentafluorophenylacetylene, and its
+
= =
conversion to [Ru{ C CX(C6F5)}(PPh3)2Cp] (X = H, alkyl, Br,
I, N2Ar [Ar = aryl], C7H7),6 were reported.
Recent studies of the redox properties of the alkynyl systems
∫
M(C CAr)(PP)Cp¢ [M = Fe, Ru, Os; PP = (PPh3)2, dppe;
Cp¢ = Cp, Cp*] groups,7–9 together with the growing spectrum of
synthetic methods available for the preparation of organometal-
lic compounds featuring alkynyl-based ligands, including
in situ desilylation/metalation10,11 and palladium and/or copper-
catalysed cross-couplings within the metal–ligand sphere,8,12–15
have led us to reconsider the synthetic chemistry of some
fluorinated analogues. Below we describe the syntheses of a
variety of complexes containing perfluorinated phenyl and pheny-
lene ring systems that illustrate the use of in situ desilyla-
tion/metallation protocols and gold-enhanced cross-coupling
reactions in the preparation of organometallic derivatives of
pentafluorophenylacetylene and 1,4-diethynyltetrafluorobenzene.
Computational studies indicate that the electronic struc-
tures of ruthenium alkynyl complexes featuring pentaflu-
orobenzene substituents and bimetallic complexes featuring
aSchool of Chemistry and Physics, University of Adelaide, Adelaide, South
Australia, 5005
bChemistry M313, SBBCS, University of Western Australia, Crawley,
Western Australia, 6009
cLaboratoire des Sciences Chimiques de Rennes, UMR 6226 CNRS-
Universite´ de Rennes 1, 35042, Rennes, France
d
´
Laboratoire de Chimie, UMR CNRS 5182, Ecole Normale Supe´rieure de
Lyon, 46 alle´e d’Italie, 69364, Lyon cedex 07, France
eDepartment of Chemistry, Durham University, South Rd, Durham, DH1
3LE, UK. E-mail: p.j.low@durham.ac.uk; Fax: + 44 191 384 4737
f
Van’t Hoff Institute for Molecular Sciences, University of Amsterdam,
Nieuwe Achtergracht 166, 1018WV, Amsterdam, The Netherlands
† CCDC reference numbers 656421, 660619–660621, 660624. For
crystallographic data in CIF or other electronic format see DOI:
10.1039/b808798a
‡ Current address: Department of Chemistry, The University of Reading,
Whiteknights, Reading, RG6 6AD UK.
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1,4-diethynyltetrafluorobenzene-based bridging ligands are com-
parable with the analogous aromatic hydrocarbon compounds.
UV-Vis-NIR spectroelectrochemical studies are consistent with
the conclusions drawn from the computational work, and indicate
that the ethynylaromatic ligands are redox non-innocent.
which fragmented by loss of F to give ions at m/z 738 (2) and
808 (3), respectively. The structures of 2 and 3 were confirmed by
X-ray studies of crystals grown from dichloromethane/hexane (see
below).
∫
Two equivalents of Me3SiC CC6F5 react with Pt2(m-
19
dppm)2Cl2 in the presence of sodium methoxide to give Pt2(m-
∫
dppm)2(C CC6F5)2 (4). The non-fluorinated analogue has been
Results and discussion
made in a similar fashion on a previous occasion.20 The IR
spectrum of 4 contains a single n(CC) band at 2079 cm-1. In
∫
Complexes derived from Me3SiC CC6F5
1
the H NMR spectrum, characteristic resonances are found for
∫
An earlier report has described the synthesis of Ru(C CC6F5)-
(PPh3)2Cp (1) in 76% yield by treatment of pentafluorophenyl-
acetylene with RuCl(PPh3)2Cp in the presence of sodium
the dppm ligand at d 4.62 (CH2) and between d 6.96 and 7.90
(Ph). In the 31P NMR spectrum the phosphine ligands give rise
to a resonance at d 2.13, with evident coupling to 195Pt [J(PPt) =
2816 Hz]. In the 19F NMR spectrum the usual three multiplets
are found at dF -143.1, -165.7 and -168.2 for the ortho-, para-
and meta-fluorines, respectively. The ES-MS contains [M + H]+ at
m/z 1541. As with the synthesis of 1, no evidence was found to
suggest that the para-fluorine of 4 underwent nucleophilic attack
by the methoxide present in the reaction mixture. This may be for
kinetic reasons, with the metallation reaction and precipitation
of the product taking place prior to fluoride substitution, but
could also be due to electron-donation from the metal-acetylide
fragment increasing the electron density at the para-carbon of the
fluoroaromatic substituent.
methoxide.5 Here, the new analogues Ru(C CC6F5)(dppe)Cp¢
∫
∫
(Cp¢ = Cp 2, Cp* 3) were synthesised by reacting Me3SiC CC6F5
with RuCl(dppe)Cp¢ in the presence of potassium fluoride in 63%
and 54% yields, respectively (Scheme 1). The latter route does
not require prior deprotection of the alkyne and therefore avoids
the additional desilylation/purification steps associated with the
isolation of the terminal acetylene from the silylated precursor.16
Elemental analyses supported by spectroscopic data confirmed the
formulations of these complexes. Thus, in the 19F NMR spectra,
the five fluorine nuclei resonate as three signals with relative
intensities 2/1/2 from AA¢MXX¢ systems.17,18 The ortho and meta
fluorines of 1 and 2 are found as multiplets at dF -142.9, -145.6 and
-166.3, -168.8, respectively, and the para-fluorines are observed
as triplets at dF -165.7, -168.3, due to coupling with the meta
fluorine nuclei [J(FF) = 21 Hz]. This coupling is also observed in
the central parts of the AA’XX’ resonance assigned to the meta-
fluorines. Replacing the Cp group by Cp* in 3 has little effect
on the resonance from the ortho-fluorine atoms which is found
at dF -145.8, although unusually, the para-fluorine resonance (dF
-169.1) is observed upfield of that from the meta-fluorine atoms
∫
Complexes derived from Au(C CC6F5)PPh3
The Pd(0)/Cu(I)-catalysed reaction between phosphine-gold(I)
alkynyls and C(sp2 or sp3)–X (X = Br, I) bonds has re-
cently been developed as a base-free analogue of the Sono-
gashira reaction, which is useful in the preparation of novel
metal-containing alkynyl and poly-ynyl derivatives.16 Using
∫
this methodology, reaction between Au(C CC6F5)(PPh3) and
(dF -168.9). Comparison of the 19F chemical shifts for HC CC6F5
Mo(∫CBr)(CO)2Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)-
∫
[d -134.2 (o-F), -149.9 (p-F), -159.6 (m-F)] with those of 2 shows
that replacement of H by the Ru(dppe)Cp moiety results in shifts
of -11.4, -18.4 and -9.2 ppm, reflecting the electron-donating
properties of the Ru centre.
In the 31P NMR spectra, characteristic resonances at dP 87.0
(2) or 81.7 (3) were found. The electrospray-mass spectra (ES-
MS) of these complexes contained M+ at m/z 756 (2) and 826 (3),
borate] gave the pentafluorophenyl-terminated C3 complex,
∫
∫
Mo( CC CC6F5)(CO)2Tp* (5) (18%) (Scheme 2). Complex 5 was
characterised by the usual array of spectroscopic methods, with
ES-MS containing [M + Na]+ at m/z 677. The IR spectrum of 5
displays two n(CC) bands at 2110 and 2061 cm-1 and two terminal
n(CO) bands at 2006 and 1926 cm-1. In the 19F NMR spectrum the
ortho- and meta-fluorines are found at dF -136.8 and -163.9, with
Scheme 1
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Scheme 2
the para-fluorine giving a triplet dF -153.7 [J(FF) = 20 Hz]. The
broadening of each line within this triplet suggests that there is
also an unresolved coupling between the para- and ortho-fluorine
nuclei.
and our attempts to synthesise bis-metalla-1,4-diethynyltetra-
fluorobenzenes by reacting monometallic (pentafluorophenyl)-
ethynyl complexes 1–3 with alkynyl anions have been so
far unsuccessful. Hence 1,4-bis[(trimethylsilyl)ethynyl]tetrafluoro-
benzene16,22 was treated with RuCl(PP)Cp¢ [where PP = (PPh3)2,
dppe; Cp¢ = Cp, Cp*] in the presence of KF to give the diruthenium
The Pd(0)/Cu(I)-catalysed reaction between Co3(m3-CBr)(m-
∫
dppm)(CO)7 and Au(C CC6F5)(PPh3) afforded dark red Co3(m3-
∫
∫
CC CC6F5)(m-dppm)(CO)7 (6) (36%) (Scheme 2), characterised
complexes 1,4-{Cp¢(PP)Ru(C C)}2C6F4 [PP = (PPh3)2, Cp¢ = Cp
by IR [n(CC) at 2122 cm-1, terminal n(CO) between 2062 and
1976 cm-1] and multinuclear NMR [CH2 at dH 3.49, 4.24, dC 29.60,
one C(sp) at dC 72.17, Ph between dH 7.18–7.73, dC 128.73–132.43,
dppm (dP 34.7) and C6F5 [dF -139.8, -158.4, -165.5 (o-, p-, m-F)]
spectroscopies, and ES-MS, with [M + Na]+ and [M + H]+ at
m/z 983 and 961, respectively, being observed. In the negative ion
ES-MS, [M - H]- at m/z 959 was observed. The structure of the
complex was also established by a single crystal X-ray diffraction
study.
(8), PP = dppe, Cp¢ = Cp (9), Cp* (10)] in 60, 26 and 63% yields,
respectively (Scheme 3). Elemental analyses and ES-MS confirmed
the formulations of these complexes with M+ found at m/z 1578
(for 8) and 1326 (9), with [M + H]+ being obtained as the highest
molecular weight ion in the MS of the most electron-rich example,
10. For each compound 8–10 the IR spectra contain two n(CC)
bands, which were closely spaced, between 2072 and 2032 cm-1. In
the 1H NMR spectra, the usual resonances for the Cp ligands are
found at dH 4.86 (8) and 4.71 (9), and for Cp* at d 1.68 (10). The
13C NMR of 10 contains resonances at dC 10.7 and 93.7 (Cp*). In
the 31P NMR spectra, characteristic resonances at dP 51.7 (8), 86.7
(9) and 80.9 (10) were found. The 19F NMR spectra each contain
only one resonance at dF -147.0 (8), -147.8 (9) and -148.0 (10),
as expected for a symmetrically disubstituted C6F4 group.
The Cadiot–Chodkiewicz reaction, in which a terminal alkyne
∫
∫
RC CH and a haloalkyne XC CR¢ are cross-coupled in the pres-
ence of a copper catalyst, is a well-known route to the preparation
21
∫
∫
of differentially substituted 1,4-buta-1,3-diynes, RC CC CR¢.
∫
The reaction between Au(C CC6F5)(PPh3) and iodoethynylfer-
∫
rocene, IC CFc, gives 1-ferrocenyl-4-pentafluorophenylbuta-1,3-
∫
∫
∫
∫
diyne, FcC CC CC6F5 (7), accompanied by some FcC CC CFc.
The composition of the former compound was readily established
from elemental analysis and the usual spectroscopic data. Thus in
the IR spectrum a single n(CC) band was observed at 2220 cm-1. In
the 13C NMR spectrum, resonances at dC 62.10, 69.53, 86.86 and
99.55 are assigned to the carbon nuclei of the butadiyne fragment.
In the 19F NMR two multiplets at dF -137.7 and -163.8 and
a triplet at dF -153.9 are found for the o-, m- and p-fluorines,
respectively. The ES-MS contains M+ at m/z 400.
∫
Ruthenium complexes derived from 1,4-(Me3SiC C)2C6H4
For purposes of comparison with the fluorinated complexes
here, it was desirable to examine the hydrocarbon analogues
∫
∫
Ru(C CPh)(PP)Cp¢ and 1,4-{Cp¢(PP)RuC C}2C6H4. All three
∫
monoruthenium complexes Ru(C CPh)(PP)Cp¢ have been re-
ported elsewhere.8,23,24 Of the diruthenium complexes only the
∫
very insoluble compound 1,4-{Cp(PPh3)2RuC C}2C6H4 (11) has
been prepared previously.25 The more soluble systems 1,4-
∫
∫
∫
{Cp(dppe)RuC C}2C6H4 (12) and 1,4-{Cp*(dppe)RuC C}2C6H4
(13) were readily prepared from reactions of 1,4-(Me3SiC C)2C6H4
∫
Ruthenium complexes derived from 1,4-(Me3SiC C)2C6F4
and two molar equivalents of the appropriate chloride precursor
RuCl(PP)Cp¢ in the presence of KF (Scheme 3). The character-
isation of these compounds was straightforward, and details of
The pentafluorophenyl ring systems in complexes such as 1–3 are
inert toward substitution reactions with common nucleophiles,
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∫
Fig. 2 Projection of a single molecule of Ru(C CC6F5)(dppe)Cp (2).
Scheme 3
the elemental analytical and spectroscopic results are given in the
Experimental section.
Molecular structures
The structures of 1, 2, 3, 6 and 10 have been determined by
single-crystal X-ray diffraction studies† and molecules of these
complexes are depicted in Fig. 1–5. Table 1 contains selected
structural parameters for all but 6, for which selected data are given
in the caption to the associated Figure, whilst Table 2 summarises
∫
Fig. 3 Projection of a single molecule of Ru(C CC6F5)(dppe)Cp* (3).
details of the data collection. The Ru(dppe)Cp¢ fragments have the
expected near-octahedral geometry, with Ru–P bond distances of
˚
˚
2.238(2)–2.2694(8) A and Ru–C(Cp) 2.215(7)–2.269(3) A. Along
˚
the carbon chain of 2 C(1)–C(2) is 1.205(9) A and C(2)–C(21) is
˚
˚
1.432(9) A, while in 3 C(1)–C(2) is 1.217(5) A and C(2)–C(21)
˚
˚
is 1.442(5) A. The Ru–C(1) distance in 2 is 1.982(7) A, similar
to that reported for Ru(C CC CSiMe3)(dppe)Cp* [1.983(2) A];
in 3 the Ru–C(1) distance is 2.000(3) A. The carbon chain of
26
˚
∫
∫
˚
2 is significantly less distorted than that of 3, with angles at
C(1,2) of 178.7(6) and 177.2(7)◦ (for 2) compared with values of
168.9(3) and 170.2(3)◦ for 3. In 10 the Ru(dppe)Cp fragment has
˚
the expected geometry, with Ru–P(1,2) 2.2542(7) and 2.2607(7) A
˚
and Ru–C(Cp) 2.223(3)–2.264(3) A; the C(1)–C(2), C(2)–C(3)
˚
separations are 1.221(3), 1.427(3) A and the Ru–C(1) distance
˚
is 1.996(2) A. The carbon chain is again somewhat distorted,
with angles at C(1,2) of 172.6(2) and 172.2(3)◦, respectively.
Surprisingly, compound 10 appears to represent the first bimetallic
∫
∫
ruthenium complex of general type LnRuC CArC CRuLn to be
structurally characterised.
Comparison of closely related complexes containing Ph and
C6F5 groups shows that there are few significant structural
∫
Fig. 1 Projection of a single molecule of Ru(C CC6F5)(PPh3)2Cp (1). In
this, and subsequent plots, hydrogen atoms have been omitted for clarity.
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∫
Fig. 5 Projection of a molecule of 1,4-{Cp*(dppe)Ru(C C)}2C6F4 (10).
C6F5 analogues [2.017(5), 2.009(3), 2.011(4) (X = H) vs. 1.991(6),
˚
1.982(7), 2.000(3) A (X = F)], while the C(2)–C(21) distances are
also shorter in two of the C6F5 compounds, but longer in the
Cp* complex [1.463(8), 1.444(5), 1.431(5) (X = H) vs. 1.421(9),
˚
1.432(9), 1.442(5) A (X = F)]. However, the differences are
only marginally significant. Within the C6X5 ring, average C–C
separations are 1.395(8), 1.396(5), 1.373(9) (X = H) vs. 1.380(6),
˚
1.373(10), 1.383(11) A (X = F).
In 6 (Fig. 4), the carbon chains of the two independent molecules
are essentially linear [C(2)–C(3)–C(131) 175.8(2), 173.5(2)◦] with
˚
C(1)–C(2) [1.403(2), 1.404(2) A] consistent with a carbon–carbon
˚
single bond and C(2)–C(3) [1.213(2), 1.208(2) A] with C(1)–C(2)
∫
Fig. 4 Projection of molecule 1 of Co3(m3-CC CC6F5)(m-dppm)(CO)7
triple bond. The Co3(m-dppm)(CO)7 clusters are similar to those
found in many related examples,15,27–30 with Co–Co 2.4763(4)–
2.4938(4), Co–P 2.2014(5)–2.2108(4) and Co–C(1) 1.893(2)–
˚
(6). Selected structural data: Bond distances (A) Co(1)–Co(2,3) 2.4781(5),
2.4810(4), Co(2)–Co(3) 2.4805(4), Co(n)–P(n) (n 1,2) 2.2014(5),
2.2035(4), Co(1)–C(1) 1.900(1), Co(2)–C(1) 1.914(2), Co(3)–C(1)
1.947(1), C(1)–C(2) 1.403(2), C(2)–C(3) 1.213(2), C(3)–C(131) 1.428(2),
=
˚
1.914(2) and 1.940(1), 1.947(1) A, the latter involving Co(3), which
is not attached to the dppm ligand.
˚
C(13n)–C(13n + 1) (av.) 1.385(9), C(13n)–F(13n) (av.) 1.343(3) A.
Bond angles (◦) Co(1)–C(1)–C(2) 136.3(1), Co(2)–C(1)–C(2) 131.4(1),
Co(3)–C(1)–C(2) 127.2(1), C(1)–C(2)–C(3) 179.1(2), C(2)–C(3)–C(131)
175.8(2), C(3)–C(131)–C(132) 121.9(1), C(3)–C(131)–C(136) 121.8(1)◦.
Molecule 2 is similar, differing only in the aromatic ring orientations.
Electrochemistry
Extensive studies of the redox properties of arylalkynyl complexes
containing M(PP)Cp¢ [M = Fe, Ru; PP = (PPh3)2, dppe; Cp¢ =
Cp, Cp* (not all combinations)] fragments have been made, with
complementary spectroscopic and computational work used to
analyse the physical and electronic structure of the redox-related
species.7–9 In the case of arylalkynyl compounds of the Group 8
metals, the extensive mixing of the metal and alkynyl frontier
orbitals leads to a significant degree of carbon ligand character in
∫
differences. Considering the three pairs: Ru(C CC6X5)(PP)Cp¢
[X = H, F; (PP)Cp¢ = (PPh3)2Cp and (dppe)Cp, (dppe)Cp*,
the Ru–P distances are experimentally the same in each pair,
although they may differ with ligand set.8,23,24 The Ru–C(1)
distance is longer in the phenylethynyl derivatives than in the
Table 1 Selected bond parameters for 1–3 and 10
Complex
1
2
3
10
˚
Bond distances/A
Ru–P(1)
Ru–P(2)
2.295(2)
2.282(2)
2.238(2)
2.260(2)
2.2694(8)
2.2592(8)
2.2542(7)
2.2607(7)
Ru–C(Cp)
(Av.)
2.232(5)–2.261(6)
2.244(11)
2.215(7)–2.250(8)
2.234(14)
2.224(3)–2.269(3)
2.25(2)
2.223(3)–2.264(3)
2.250(16)
Ru–C(1)
C(1)–C(2)
1.991(6)
1.225(9)
1.982(7)
1.205(9)
2.000(3)
1.217(5)
1.996(2)
1.221(3)
C(2)–C(21)
C(2n)–F(2n)
(Av.)
1.421(9)
1.329(8)–1.362(12)
1.344(14)
1.432(9)
1.329(9)–1.353(10)
1.340(10)
1.442(5)
1.338(5)–1.352(5)
1.344(6)
1.427(3)
1.342(3), 1.356(3)
1.349(10)
Bond angles/◦
P(1)–Ru–P(2)
P(1)–Ru–C(1)
P(2)–Ru–C(1)
Ru–C(1)–C(2)
C(1)–C(2)–C(21)
100.31(5)
92.3(2)
87.4(2)
173.0(5)
169.2(6)
83.48(6)
87.2(2)
81.6(2)
178.7(6)
177.2(7)
82.44(3)
89.12(9)
87.62(9)
168.9(3)
170.2(3)
82.62(3)
86.38(7)
85.45(7)
172.6(2)
172.2(3)
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Table 2 Crystal data and refinement details†
Complex
1
2
3
6
10
Formula
MW
Crystal system
C49H35F5P2Ru·0.5C6H6
C39H29F5P2Ru
755.67
Orthorhombic
P212121
8.988(1)
15.065(2)
23.420(3)
—
—
—
3171.2(7)
4
1.583
C44H39F5P2Ru
825.8
Monoclinic
C41H22Co3F5O7P2
960.32
Triclinic
¯
P1
C82H78F4P4Ru2
1465.55
Monoclinic
P21/n
10.982(1)
18.486(2)
17.193(2)
—
93.839(2)
—
3482.6(6)
2
1.398
62
0.58
0.92
0.48 ¥ 0.32 ¥ 0.12
38966
11272 (0.033)
8907
0.036
920.88
Monoclinic
P21/n
Space group
P21/c
˚
a/A
10.1626(7)
24.5128(2)
17.0993(8)
—
96.323(5)
—
4233.8(4)
4
1.445
8.605(1)
25.438(3)
17.212(2)
—
100.864(2)
—
3700.1(7)
4
1.482
11.617(1)
17.643(2)
19.108(3)
97.855(9)
91.445(11)
93.438(7)
3870.4(8)
4
1.648
68
1.43
0.92
0.38 ¥ 0.28 ¥ 0.24
76417
29976 (0.024)
20530
0.032 (R1)
0.083 (wR2)
100
˚
b/A
˚
c/A
a/◦
b/◦
g /◦
3
˚
V/A
Z
rc/g cm-3
◦
2qmax
/
58
0.50
0.92
58
0.65
0.91
58
0.57
0.91
m(Mo-Ka)/mm-1
Tmin/max
Crystal dimensions/mm
Ntot
0.26 ¥ 0.21 ¥ 0.05
92469
11272 (0.067)
11272
0.068
0.085
100
0.23 ¥ 0.15 ¥ 0.09
30061
4570 (0.048)
4127
0.048
0.067
170
0.36 ¥ 0.13 ¥ 0.07
33123
9336 (0.043)
7506
0.044
0.080
170
N(Rint
No
)
R
Rw
T/K
0.077
150
the HOMOs of the resulting radical cations.8,9 Table 3 collects elec-
about by the electron-withdrawing fluoro substituents. The first
oxidation potentials follow the same trends as observed for the
monometallic complexes, with oxidation of the fluorinated species
being less thermodynamically favourable when compared with the
hydrocarbon analogues.
trochemical data for the ruthenium s-alkynyl complexes 2–3, 8–13
∫
and the monoruthenium complexes Ru(C CPh)(PP)Cp¢ described
above, referenced against the ferrocene/ferrocenium couple. Given
the contribution from the aryl ring to the redox-active orbital
in these systems, it is unsurprising that perfluorination of the
arylalkynyl ligand leads to less thermodynamically favourable
oxidation (e.g., 2 +0.10 V, 3 -0.04 V) than found in the hydro-
Electronic structure calculations
∫
carbon analogues such as Ru(C CPh)(dppe)Cp (-0.08 V) and
In order to more fully probe the influence of perfluorination on the
9,31,32
∫
Ru(C CPh)(dppe)Cp* (-0.26 V).
The fluorinated bimetallic
∫
electronic structure of compounds such as Ru(C CC6X5)(PP)Cp¢
complexes 8–10 and the hydrocarbon analogues 11–13 each
undergo two reversible oxidation events, E1 and E2 with DEp =
|E2 - E1| ca. 200–300 mV. The larger DEp values are generally
associated with the complexes featuring perfluorinated bridges,
and indicate the greater stability of the mono-oxidised species with
respect to disproportionation. This is likely a consequence of the
higher thermodynamic barrier to the second oxidation brought
∫
and 1,4-{Cp¢(PP)RuC C}2C6X4 (X = H, F), a series of density
functional theory (DFT) calculations (B3LYP/3–21G*) were
∫
carried out on the model systems Ru(C CC6F5)(PH3)2Cp (1-
9
∫
∫
F), Ru(C CPh)(PH3)2Cp (1-H), 1,4-{Cp(PH3)2RuC C}2C6F4 (8-
∫
F) and 1,4-{Cp(PH3)2RuC C}2C6H4 (11-H). Results from the
structural optimisations are summarised in Table 4, with relevant
data from single crystal X-ray diffraction experiments of suitable
compounds for comparison. Details of the orbital energies and
compositions are summarised in Tables 5 and 6, and important
orbitals are illustrated in Fig. 6–9. Whilst the basis set employed
is relatively small, it has proven to be entirely satisfactory
Table 3 Electrochemical data from 2–3, 8–13 and related systemsa
Compound
E1
E2
DEp
∫
against other, larger, basis sets for Ru(C CC6X5)(PP)Cp¢ type
compounds.9
2
3
0.10
-0.04
0.11
—
—
—
—
—
—
—
—
The electronic structures of pseudo-octahedral d6 metal alkynyl
complexes such as 1-H have been studied on previous occasions
at various levels of theory,7–9 and only pertinent details are sum-
marised here for completeness. The highest occupied molecular
orbitals of the monometallic systems 1-H and 1-F essentially com-
prise the antibonding combinations of the orthogonal acetylene
p-system with metal d-orbitals of appropriate symmetry (Fig. 6
and 7). The acetylide phenyl substituent is oriented either orthog-
onally (1-H) or co-planar (1-F) with a plane bisecting the P–Ru–P
angle. However, the barrier to rotation around the C(2)–C(21)
bond is small (estimated at 0.3 and 0.4 kcal mol-1 for 1-H and 1-F,
respectively, at B3LYP/3–21G*) and the preferential orientation
b
∫
Ru(C CPh)(PPh3)2Cp
∫
Ru(C CPh)(dppe)Cp
Ru(C CPh)(dppe)Cp*
8
9
10
11
12
13
-0.08
-0.26
-0.09
-0.17
-0.35
-0.30
-0.32
-0.50
∫
—
—
0.21
0.11
-0.03
-0.01
-0.09
-0.22
0.30
0.28
0.32
0.29
0.23
0.28
a CH2Cl2/0.1 M [NBu4]BF4, Pt microdisk working, Pt wire counter, Pt
wire pseudoreference electrodes, potentials in Volts vs. FeCp2/[FeCp2]+,
via reference to FeCp2, FeCp*2 or CoCp2+ internal standards. b Data from
ref. 9.
6768 | Dalton Trans., 2008, 6763–6775
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Table 4 Optimised structural data from 1-H, 1-F, 8-F and 11-H, with crystallographic data from related systems
a
∫
1-H
Ru(C CPh)(PPh3)2Cp
1-F
1
8-F
8
11-H
Ru–C(1)
Ru–P
2.018
2.278
1.228
1.426
—
2.016(3)
2.285(1), 2.303(1)
1.215(4)
1.456(4)
—
2.001
2.284
1.226
1.406
—
1.991(6)
2.295(2), 2.282(2)
1.225(9)
1.421(9)
—
2.005
2.282
1.226
1.407
180.0
1.996(2)
2.2542(7), 2.2607(7)
1.221(3)
1.427(3)
180
2.018
2.277
1.228
1.423
158.9
C(1)–C(2)
C(2)–C(21)
b
q
a Ref. 23a b q = P(1)–Ru(1) ◊ ◊ ◊ Ru¢–P(1)¢.
Table 5 The energy (E/eV) and composition of selected frontier molec-
ular orbitals in 1-F and 1-H
1-F
MO
E
Cp PH3
Ru Ca
Cb
C6F5
109
108
107
106
105
104
103
102
L + 4
L + 3
L + 2
L + 1
LUMO -1.05
HOMO -5.18
H - 1
H - 2
-0.02
-0.19
-0.43
-0.66
0
3
17
2
24
7
0
0
0
0
8
15
0
10
6
10
0
0
1
1
100
0
1
76
0
23
1
21
14
2
27
3
5
11
76
59
4
49
34
60
43
0
23
19
14
-5.68
-6.20
8
22
1
1-H MO
E
Cp PH3
Ru Ca
Cb
C6H5
89
88
87
86
85
84
83
82
L + 4
L + 3
L + 2
L + 1
0.57
0.09
-0.03
-0.15
0
2
3
16
24
2
8
26
2
6
0
10
6
8
0
16
10
6
0
1
2
0
92
48
26
0
0
29
4
12
11
13
27
1
4
14
27
54
62
50
30
46
46
Fig. 6 Frontier orbitals of 1-H. Contour values are plotted at 0.04
(e bohr-3)1/2
.
LUMO -0.78
0
HOMO -4.91
22
28
1
H - 1
H - 2
-5.09
-5.72
ligand resulting in only a small decrease in the ligand character.
Thus, for either system descriptions of the redox chemistry in
terms of metal-localised behaviour is likely an oversimplification.
In contrast to the delocalised nature of the HOMO, in both 1-H
and 1-F the LUMO is centred on the metal fragment, without any
significant contribution from the arylalkynyl moiety (Fig. 6 and 7).
The aryl/alkynyl p* systems lie above these empty metal orbitals,
and, as would be expected, the p*-system of the fluorinated ring is
somewhat lower in energy than that of the analogous orbital from
the aromatic hydrocarbon (Table 6).
6
seems to depend more upon the level of theory employed or the
starting point for the geometry optimisation than any significant
electronic factor. In either case, the repulsive interactions between
∫
the filled M–C C and phenyl fragment orbitals destabilise the
more delocalised orbital, and therefore it is this that comprises the
HOMO. The contribution from the arylalkynyl fragment to the
HOMO is not negligible (ca. 56–67%),9 with fluorination of the
Table 6 The energy (E/eV) and composition of selected frontier molecular orbitals in 8-F and 11-H
8-F
MO
E
Cp(1)
PH3(1)
Ru(1)
Ca(1)
Cb(1)
C6F4
Cb(2)
Ca(2)
Ru(2)
PH3(2) Cp(2)
168
167
166
165
164
163
162
161
L + 4
L + 3
L + 2
L + 1
LUMO
HOMO
H-1
-0.16
-0.17
-0.48
-0.79
-0.79
-4.49
-5.33
-5.37
9
8
1
24
0
3
5
3
7
7
1
27
0
1
2
2
30
29
3
49
0
14
24
30
4
4
12
0
0
9
2
4
0
1
1
0
0
1
63
0
0
25
10
2
0
1
1
0
4
4
12
0
0
9
2
4
29
30
3
7
7
1
0
27
1
2
9
9
1
0
24
3
5
0
0
0
49
14
24
28
11
12
11
11
12
10
H-2
2
3
11-H
MO
E
Cp(1)
PH3(1)
Ru(1)
Ca(1)
Cb(1)
C6H4
Cb(2)
Ca(2)
Ru(2)
PH3(2) Cp(2)
152
151
150
149
148
147
146
145
L + 4
L + 3
L + 2
L + 1
LUMO
HOMO
H-1
-0.02
-0.03
-0.04
-0.66
-0.67
-4.17
-5.11
-5.14
1
9
7
0
24
2
5
2
7
5
0
27
1
2
4
11
4
3
0
0
11
3
6
2
0
0
0
0
9
13
14
59
0
0
0
0
30
8
2
2
0
0
0
0
9
13
11
11
4
4
0
0
11
3
5
4
2
6
7
27
0
1
2
1
1
7
9
24
0
2
5
2
36
28
0
50
12
23
30
28
36
50
0
12
23
23
H-2
2
2
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The calculated electronic structures of the bimetallic systems
11-H and 8-F, which are similar to each other, merit consideration
and discussion. Geometry optimisations for 11-H and 8-F show
minima (type A) with the phenyl ring of the bridging ligand
orthogonal to the plane bisecting the P–Ru–P angles and minima
(type B) with the phenyl ring of the bridging ligand co-planar with
the plane bisecting the P–Ru–P angle. Both minima A and B have
the same energies at B3LYP/3–21G* for 11-H and 8-F. Similar
behaviour for related systems has been noted elsewhere.33 Here
we focus on type A minima in detail for 11-H and 8-F, although
similar conclusions for structure type B may also be made.
The HOMOs of 11-H and 8-F are, in each case, of comparable
composition to those of the mononuclear models (Fig. 8 and
9), being delocalised over the metal centres, alkynyl fragment
and aromatic ring system. Interestingly, the HOMO in 11-H
and 8-F is 65–70% diethynyl aromatic ligand in character, and
consequently the compounds are best described in terms of an
organic diethynylarylene featuring strong p-donating substituents
[the Ru(PP)Cp¢ fragments]. In each case, the HOMO is well-
separated in energy from the other occupied orbitals, in agreement
with the electrochemical observation of two anodic events. The
HOMO-1 can be described in terms of the various other in-
and out-of-phase combinations of the metal (d) and acetylide (p)
orbitals, and being lower in energy in the case of the fluorinated
derivative (Fig. 8 and 9, Table 6). Within the unoccupied orbital
manifold the diethynylbenzene p* system is interleaved within
the unoccupied metal d orbitals, with the fluorinated system
naturally lying lower in energy than the hydrocarbon analogue
(Table 6). Interestingly, although Koopmans’ theorem has no
direct correlation with DFT-based methods of electronic structure
calculation, the HOMO in 11-H is higher in energy than the
HOMO in 8-F. This energy order maps with the differences in
redox properties of 11 and 8, and supports the fairly intuitive
observation than the introduction of the perfluoroaryl group
leads to less thermodynamically favourable oxidation processes
(vide supra).
Fig. 7 Frontier orbitals of 1-F. Contour values are plotted at 0.04
(e bohr-3)1/2
.
Fig. 8 Frontier orbitals of 8-F. Contour values are plotted at 0.04
(e bohr-3)1/2
.
UV-Vis-NIR spectroelectrochemistry
To provide an experimental check of the key conclusions drawn
from the computational work (i.e. that the electronic structures of
∫
the bimetallic ruthenium complexes 1,4-{Cp¢(PP)RuC C}2C6X4
(X = H, F) are largely insensitive to fluorination of the alkynylaryl
ring system, and that the HOMOs contain a very large amount
of alkynylaryl character), UV-Vis-NIR spectroelectrochemical
studies were conducted on complexes 10 and 13 (Fig. 10), chosen
as samples representative of the series 8–13. The spectra of the
neutral complexes 10 and 13 are similar, each being dominated by
an intense band at 27100 (13) or 24900 (10) cm-1. The red-shift of
this band on fluorination of the phenylene ring is consistent with
the assignment of the band to an MLCT transition, or perhaps
more accurately to a bridge-based p–p* transition, albeit with
the p-orbitals of the bridge admixed with some metal character
(ML-LCT). In each case, this characteristic band collapses upon
one-electron oxidation and is replaced by structured bands or
composite band envelopes in the region 20000–17000 cm-1 and
8000–5000 cm-1.
Fig. 9 Frontier orbitals of 11-H. Contour values are plotted at 0.04
(e bohr-3)1/2
.
In general, perfluorination has little effect on the gross descrip-
tion of the electronic structure of the arylalkynyl complexes of
ruthenium described here, save to stabilise the orbital manifold
to some extent. A small elongation of the calculated Ru–P
bond lengths is not reproduced within the level of precision of
23
∫
the structure determinations of Ru(C CPh)(PPh3)2Cp and 1.
However, the contraction of the Ru–C(1) bond length observed
upon comparison of the optimised geometries of 1-H and 1-F is
reflected at the limit of precision in the experimentally determined
structures, and likely arises from the greater electrostatic attraction
of the Ru and C(1) centres in the case of the fluorinated compound.
Both [10]+ and [13]+ feature structured bands in the visible
region that are similar to those observed in related radical
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the components in the NIR band envelopes of [10]+ and [13]+
provides yet more evidence for the electronic similarity of these
compounds. The absorption profile is red-shifted in the case of the
fluorinated ring system, consistent with transfer of electron density
to the phenylene-based orbitals in the transitions responsible for
these bands, providing further evidence for the involvement of
the phenylene ring in the redox active orbital. The deconvoluted
NIR bands are also considerably narrower than predicted from
the Hush model for weakly-coupled mixed-valence compounds,37
and too intense to be simple dd bands associated with a d5 metal
centre. Therefore, the lower energy component is assigned to the
[HOMO-1] to SOMO transition, which has metal-ethynyl (d-p) to
aryl (p) character. The higher energy component can be attributed
to a transition from a lower-lying, more metal based orbital (or
orbitals) to the SOMO (i.e. an M-MLCT transition).
Although an electrogenerated sample of the dication [10]2+
decomposed before a reliable spectrum could be obtained, the UV-
Vis-NIR spectrum of the dication [13]2+ was satisfactorily obtained
by controlled potential electrolysis in a spectroelectrochemical
cell, as evidenced by the sequential re-reduction through [13]+
Fig. 10 The UV-Vis-NIR spectra of [10]n+ (top) and [13]n+ (bottom)
(CH2Cl2/0.1M NBu4BF4).
to [13]. The spectrum of [13]2+ (Fig. 10) is similar in profile to that
+
complexes34 and compounds35 in which the phenylene ring systems
are intimately involved in supporting the unpaired electron. When
this experimental observation is considered alongside the DFT
results, it is reasonable to describe oxidation of the ruthenium
∫
of [Ru(C CC6H4Me-4)(dppe)Cp*] , and by analogy the major
visible band in [13]2+ can be assigned to a metal-to-metal/ligand
(M-MLCT) transition.9 A weaker band is also present in the
NIR region of [13]2+, which is similar to that observed for the
analogous mononuclear system [3]+ and may therefore be assigned
to a similar transition between approximately orthogonal orbitals
with significant metal d/ethynyl p character.9
∫
complexes 1,4-{Cp¢(PP)RuC C}2C6X4 in terms of depopulation
of the HOMO to give a SOMO of comparable character to those
depicted in Fig. 8 and 9. The band envelope in the NIR region is
similar in each of [10]+ and [13]+, and can be deconvoluted into
the sum of two Gaussian-shaped components (Fig. 11), which
contrasts with more complex deconvolutions associated with the
Taken as a whole, these UV-Vis-NIR spectroscopic data support
the conclusions drawn from the DFT work, and indicate that
∫
the frontier/redox active orbitals in 1,4-{Cp¢(PP)RuC C}2C6X4
systems are heavily centred on the bridging ligand. It is therefore
not appropriate to discuss the properties of these compounds in
terms of mixed-valence models, but rather they should be regarded
as further examples of bimetallic compounds featuring redox
“non-innocent” bridging ligands.38
NIR spectrum of the strongly coupled mixed valence complex
+
∫
1,4-[{Cp*(dppe)FeC C}2C6H4] due to the pronounced “cut-off”
on the high energy side, and potential complications arising from
multiple IVCT transitions.36 The almost identical band-shapes of
Conclusions
This work has demonstrated the efficient syntheses of several com-
plexes featuring mono- and di-ethynyl derivatives of perfluoro-
inated phenyl and phenylene ring systems, by treating the readily
available SiMe3-protected alkyne with equivalent amounts of the
metal-halide precursor either in a fluoride- or NaOMe-initiated
desilylation/metallation reaction sequence. Whilst nucleophilic
substitution reactions are common in the chemistry of perflu-
oroaromatics, the introduction of a strong inductive electron-
donating metal alkynyl fragment effectively turns off this reaction
pathway. Gold-modified Sonogashira and Cadiot–Chodkiewicz
coupling protocols are also effective as chain extension reactions
involving perfluorophenyl rings. In the case of the monometal-
lic (1–3) and bimetallic (8–13) ruthenium alkynyl complexes,
perfluorination of the alkynyl-based ligand does not greatly
affect the overall electronic structure of the compounds. Rather,
perfluorination leads to a small stabilisation of the orbital mani-
fold, and consequently less thermodynamically favourable oxida-
tion. Interestingly, calculations reveal a significant (ca. 60–70%)
contribution from the ethynyl aromatic moiety to the HOMOs
in the ruthenium systems. This prediction is supported by
Fig. 11 The NIR region of [10]+ (top) and [13]+ (bottom) showing the
deconvolution of the absorption envelope into a sum of two Gaussian
1
-1
shaped components ([10]+ : nmax = 5352 cm , Dn 2 = 1114 cm-1,
¯
¯
1
2
e = 6875 dm3 mol-1 cm ; nmax= 6584 cm , Dn = 2834 cm-1, e =
-1
-1
¯
¯
1
2
6432 dm3 mol-1 cm-1. [13]+ nmax= 5630 cm , Dn = 1102 cm-1, e =
-1
¯
¯
1
2
12410 dm3 mol-1 cm ; nmax= 6874 cm , Dn = 2700 cm-1, e =
-1
-1
¯
¯
16553 dm3 mol-1 cm-1).
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∫
Derivatives of Me3SiC CC6F5
UV-Vis-NIR spectroscopy, and raises questions about the nature
of the oxidation events (metal- vs. ligand- centred) and “mixed
valence” character of many similar ruthenium/alkynyl based
systems. Further experiments directed at probing this point are
in progress and will be reported elsewhere.
∫
∫
(a) Ru(C CC6F5)(dppe)Cp (2). A mixture of Me3SiC CC6F5
(300 mg, 1.13 mmol), RuCl(dppe)Cp (456 mg, 0.76 mmol) and
KF (44 mg, 0.15 mmol) in MeOH (20 ml) was heated under reflux
for 5 h. The resulting yellow precipitate was collected and washed
∫
with MeOH followed by hexane to give Ru(C CC6F5)(dppe)Cp
Experimental
(2) (575 mg, 63%). Anal. Calcd (C39H29F5P2Ru): C, 61.99; H, 3.87;
M, 755. Found: C, 61.93; H, 3.83. IR (Nujol, cm-1): n(CC) 2097
m, 2070 w. 1H NMR (C6D6): d 2.16, 2.71 (2 m, 2 ¥ 2H, CH2CH2),
4.73 (s, 5H, Cp), 6.95–7.99 (m, 24H, Ph). 13C NMR: d 27.8 [t,
J(CP) 23 Hz, CH2CH2], 83.0 (s, Cp), 126.1–142.5 (m, Ph). 19F
NMR: d -145.6 (m, 2F, o-F), -168.3 [t, J(FF) = 21 Hz, 1F, p-F],
-168.8 (m, 2F, m-F). 31P NMR: d 87.0 (s, dppe). ES-MS (MeOH +
NaOMe, m/z): 779, [M + Na]+; 756, [M + H]+; 738, [M - F]+; 593,
[Ru(CO)(dppe)Cp]+; 565, [Ru(dppe)Cp]+.
General
All reactions were carried out under dry nitrogen, although
normally no special precautions to exclude air were taken during
subsequent work-up. Common solvents were dried, distilled under
nitrogen and degassed before use. Separations were carried out
by preparative thin-layer chromatography on glass plates (20 ¥
20 cm2) coated with silica gel (Merck, 0.5 mm thick).
∫
(b) Ru(C CC6F5)(dppe)Cp* (3). In a procedure similar to that
Instruments
∫
used for 2, Me3SiC CC6F5 (200 mg, 0.76 mmol), RuCl(dppe)Cp*
(508 mg, 0.76 mmol) and KF (44 mg, 0.76 mmol) and MeOH
IR spectra were obtained on a Bruker IFS28 FT-IR spectrometer
from samples mounted between NaCl windows. NMR spectra
were recorded on a Varian 2000 instrument (1H at 300.13 MHz,
13C at 75.47 MHz, 31P at 121.503, 19F at 282.39 MHz). Unless
otherwise stated, samples were dissolved in CDCl3 or C6D6
contained in 5 mm sample tubes. Chemical shifts are given in
ppm relative to internal SiMe4 for 1H and 13C NMR spectra
and external H3PO4 for 31P NMR spectra. 19F NMR spectra
were referenced to CFCl3, with internal C6F6 (dF -164.9) as the
standard. Electrospray mass spectra (ES-MS) were obtained from
samples dissolved in MeOH unless otherwise indicated. Solutions
were injected into a Fisons VG Platform II spectrometer via
a 10 ml injection loop. Nitrogen was used as the drying and
nebulising gas. NaOMe was used as an aid to ionisation when
required.39 Peaks listed are the highest intensity ions in the isotopic
envelopes. Electrochemical samples (1 mM) were dissolved in
CH2Cl2 containing 0.1 M [NBu4]BF4 as the supporting electrolyte.
Cyclic voltammograms were recorded using a PAR Model 263
potentiostat and a cell with all Pt electrodes, and reported
against ferrocene (FeCp2/[FeCp2]+ = +0.00 V). Under these con-
ditions, the decamethylferrocene/decamethylferrocenium couple
is -0.53 V, and cobaltocene/cobaltocenium -1.34 V. Elemental
analyses were by CMAS, Belmont, Vic., Australia. Details of the
spectroelectrochemical cell and conditions have been published
elsewhere.9
∫
(20 ml) gave a pale green precipitate of Ru(C CC6F5)(dppe)Cp*
(3) (339 mg, 54%). Anal. Calcd (C44H39F5P2Ru): C, 64.00; H, 4.76;
M, 826. Found: C, 63.98; H, 4.80. IR (Nujol, cm-1): n(CC) 2078
m, 2033 s. 1H NMR (C6D6): d 1.66 (s, 15H, Cp*), 2.01, 2.81 (2 m,
2 ¥ 2H, CH2CH2), 7.02–7.87 (m, 20H, Ph). 13C NMR: d 10.6 (s,
∫
C5Me5), 29.9 [t, J(CP) = 23 Hz, CH2CH2], 92.7 (s, C C), 93.84
(s, C5Me5), 127.1–144.7 (m, Ph). 19F NMR: d -169.1 [t, J(FF) =
21 Hz, 1F, p-F], -168.9 (m, 2F, p-F), -145.8 (m, 2F, o-F). 31P NMR:
d 81.7 (s, dppe). ES-MS (MeOH + NaOMe, m/z): 848, [M + Na]+;
827, [M + H]+; 808, [M - F]+; 662, [Ru(CO)(dppe)Cp*]+; 635,
[Ru(dppe)Cp*]+.
∫
(c) Pt2(l-dppm)2(C CC6F5)2 (4). To a stirred suspension of
Pt2(m-dppm)2Cl2 (100 mg, 0.08 mmol) in NaOMe [from Na (50 mg)
∫
in MeOH (10 ml)] was added an excess of Me3SiC CC6F5 (50 mg).
This mixture was stirred at r.t. for 6 h before the resulting
precipitate was collected and washed with MeOH followed by
∫
hexane to give Pt2(m-dppm)2(C CC6F5)2 (6) (33 mg, 26%). Anal.
Calcd (C66H44F10P4Pt2): C, 51.44; H, 2.88; M, 1540. Found: C,
51.39; H, 2.80. IR (Nujol, cm-1): n(CC) 2079 m. 1H NMR (C6D6):
d 4.62 (m, 4H, 2 ¥ CH2), 6.96–7.90 (m, 40H, Ph). 19F NMR: d
-168.2 (m, 2F, m-F), -165.7 [t, J(FF) = 21 Hz, 1F, p-F], -143.1
(m, 2F, o-F). 31P NMR: d 2.1 [s, dppm, J(PtP) = 2816 Hz]. ES-MS
(MeOH, m/z): 1541, [M + H]+.
∫
Derivatives of Au(C CC6F5)(PPh3)
Reagents
∫
∫
(a) Mo( CC CC6F5)(CO)2Tp* (5)
The compounds RuCl(dppe)Cp*,10d Me3SiC CC6F5, 1,4-(Me3-
16
∫
∫
∫
SiC C)2C6F4,
Pt2(m-dppm)2Cl2,19 Ru(C CC6F5)(PPh3)2Cp,
16a,22
5
A
mixture of Au(C CC6F5)(PPh3) (60 mg, 0.09 mmol),
∫
1,4-{Cp(PPh3)2Ru(C C)}2C6H4 (11),40 RuCl(dppe)Cp,41 RuCl-
Mo(∫CBr)(CO)2Tp* (50 mg, 0.09 mmol), Pd(PPh3)4 (15 mg,
0.01 mmol) and CuI (5 mg, 0.02 mmol) in thf (10 ml) was stirred at
r.t. for 2 h. The solvent was then removed and the residue purified
by preparative t.l.c. using acetone–hexane (3 : 7, v/v) as eluent.
∫
(PPh3)2Cp,42 Mo(∫CBr)(CO)2Tp*,43 Pd(PPh3)4,44 Co3(m3-CBr)(m-
dppm)(CO)7,30a IC CFc, Au(C CC6F5)(PPh3) and Ru(C
45
46
∫
∫
∫
CPh)(dppe)Cp¢ (Cp¢ = Cp, Cp*)31 were all prepared as described
The major fraction was collected as a green band which contained
previously.
-1
∫
Mo(∫CC CC6F5)(CO)2Tp* (5) (11 mg, 18%). IR (Nujol, cm ):
n(CC) 2110 w, 2061 w, n(CO) 2006 s, 1926 s. 1H NMR (CDCl3):
d 2.33(s, 6H, pz-Me), 2.38 (s, 6H, pz-Me), 2.56 (s, 6H, pz-Me),
5.73 (s, 1H, H4), 5.89 (s, 2H, H4). 13C NMR: d 12.8, 14.8, 15.9
∫
Ru(C CC6F5)(PPh3)2Cp (1)
A sample of this complex was obtained as previously described,5
and recrystallised from dichloromethane/hexanes for the crystal-
lographic study.
∫
(3 ¥ s, pz-CMe), 94.1, 108.9 (2 s, C C), 106.7/107.5, 144.9/145.6,
151.55/151.60 (6 ¥ s, pz-ring C), 227.4 (s, CO), 248.8 (s, Mo C).
∫
6772 | Dalton Trans., 2008, 6763–6775
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©

View Article Online
19F NMR: d -136.8 (m, 2F, o-F), -153.7 [t, J(FF) = 21 Hz, 1F,
p-F], -163.9 (m, 2F, m-F). ES-MS (MeOH + NaOMe, m/z): 677,
[M + Na]+; 487, [MC6F5]+.
2 ¥ 2H, CH2CH2), 4.71 (s, 5H, Cp), 6.91–7.99 (m, 20H, Ph).
13C NMR (CDCl3): d 32.2 (m, CH2CH2), 88.4 (s, Cp), 126.0–
133.8 (m, Ph). 19F NMR (C6D6): d -147.8 (s, C6F4). 31P NMR
(C6D6): d 86.7 (s, dppe). ES-MS (MeCN, m/z): 1326, M+; 605,
[Ru(NCMe)(dppe)Cp]+; 565, [Ru(dppe)Cp]+.
∫
(b) Co3(l3-CC CC6F5)(l-dppm)(CO)7 (6).
A mixture of
∫
Au(C CC6F5)(PPh3) (60 mg, 0.09 mmol), Co3(m3-CBr)(m-
dppm)(CO)7 (30 mg, 0.09 mmol), Pd(PPh3)4 (15 mg, 0.01 mmol)
and CuI (5 mg, 0.02 mmol) in thf (10 ml) was stirred at r.t.
for 2 h. Solvent was removed and the residue was purified
by preparative t.l.c. (acetone–hexane, 3 : 7, v/v). The major
fraction was collected as a brown-green band (Rf = 0.52) to give
∫
(c) 1,4-{Cp*(dppe)Ru(C C)}2C6F4 (10). Similarly, from 1,4-
∫
(Me3SiC C)2C6F4 (26 mg, 0.07 mmol), RuCl(dppe)Cp* (100 mg,
0.15 mmol) and KF (8 mg, 0.15 mmol) in thf (5 ml) and MeOH
∫
(20 ml) was obtained yellow 1,4-{Cp*(dppe)Ru(C C)}2C6F4 (10)
(65 mg, 63%). Anal. Calcd (C82H78F4P4Ru2): C, 67.20; H, 5.36; M,
1466. Found: C, 67.21; H, 5.40. IR (Nujol, cm-1): n(CC) 2063 m,
∫
Co3(m3-CC CC6F5)(m-dppm)(CO)7 (6) (10 mg, 36%) as dark red
1
2032 m. H NMR (C6D6): d 1.68 (s, 15H, Cp*), 1.99, 2.88 (2 m,
crystals (CH2Cl2/pentane). Anal. Found: C, 51.30; H, 2.25. Calcd
(C41H22Co3F5O7P2): C, 51.28; H, 2.31; M, 960. IR (Nujol, cm-1):
n(CC) 2122 w, n(CO) 2062 s, 2015 s, 1976 (sh). 1H NMR (CDCl3):
d 3.49, 4.24 (2 m, 2 ¥ 1H, CH2), 7.18–7.73 (m, 20H, Ph). 13C
2 ¥ 2H, CH2CH2), 7.03–7.95 (m, 20H, Ph). 13C NMR (CDCl3): d
10.7 (s, C5Me5), 30.1 (m, CH2CH2), 93.7 (s, C5Me5), 95.9 (s, br,
RuC), 127.9–147.8 (m, Ph). 19F NMR (C6D6): d -148.0 (s, C6F4).
31P NMR (C6D6): d 80.9 (s, dppe). ES-MS (MeCN, m/z): 1467,
[M + H]+; 675, [Ru(NCMe)(dppe)RuCp*]+; 635, [Ru(dppe)Cp*]+.
∫
NMR: d 29.6 (s, CH2), 72.2 (s, C C), 128.7–132.4 (m, Ph + C6F5).
19F NMR: d -139.8 (m, 2F, o-F), -158.4 [t, J(FF) = 21 Hz, 1F,
p-F], -165.5 (m, 2F, m-F). 31P NMR: d 34.7 (s, br, dppm). ES-MS
(MeOH + NaOMe, m/z): 982, [M + Na]+; 960, M+.
∫
Derivatives of 1,4-(Me3SiC C)2C6H4
∫
∫
∫
∫
(c) FcC CC CC6F5 (7). A mixture of Au(C CC6F5)(PPh3)
(a) 1,4-{Cp(dppe)Ru(C C)}2C6H4 (12). A mixture of 1,4-
∫
∫
(60 mg, 0.09 mmol), IC CFc (30 mg, 0.09 mmol), Pd(PPh3)4
(Me3SiC C)2C6H4 (50 mg, 0.19 mmol), RuCl(dppe)Cp (222 mg,
(15 mg, 0.01 mmol) and CuI (5 mg, 0.02 mmol) in thf (10 ml)
was stirred at r.t. for 2 h. The solvent was then removed and
the residue purified by preparative t.l.c. using acetone-hexane
(3:7, v/v) as eluent. The major fraction was collected as a bright
0.37 mol) and KF (21 mg, 0.37 mmol) in MeOH (30 ml)
was heated under reflux for 16 h. The yellow precipitate was
collected and washed with MeOH, Et2O and hexane to give
∫
1,4-{Cp(dppe)Ru(C C)}2C6H4 (12) (69 mg, 30%). Anal. Calcd
∫
∫
orange band containing FcC CC CC6F5 (7) (19 mg, 50%). Anal.
Calcd (C20H9F5Fe): C, 60.04; H, 2.27; M, 400. Found: C, 59.96; H,
(C72H62P4Ru2): C, 69.00; H, 4.99; M, 1254. Found: C, 68.98; H,
5.06. IR (Nujol, cm-1): n(CC) 2072 m, 2044 (sh). 1H NMR (C6D6):
d 1.96, 2.54 (2 m, 2 ¥ 2H, CH2CH2), 4.26 (s, 10H, Cp), 6.75–
7.97 (m, 44H, Ph and C6H4). 31P NMR: d 87.0 (s, dppe). ES-MS
(MeOH + NaOMe, m/z): 1277, [M + Na]+; 1255, [M + H]+.
1
2.15. IR (Nujol, cm-1): n(CC) 2220 m. H NMR (C6D6): d 4.29,
4.58 (2 ¥ m, 9H, Cp + C5H4). 13C NMR: d 62.1, 69.5, 86.9, 99.6
(4 s, C C), 70.4, 70.8, 72.9 (3 s, C5H4), 132.3–137.5 (m, Ph). 19F
∫
NMR: d -137.7 (m, 2F, o-F), -153.9 [t, J(FF) = 21 Hz, 1F, p-F],
∫
(b) 1,4-{Cp*(dppe)Ru(C C)}2C6H4 (13). A suspension of
-163.8 (m, 2F, m-F). ES-MS (MeOH, m/z): 400, M+. A minor
∫
RuCl(dppe)Cp* (500 mg, 0.747 mmol), 1,4-(Me3SiC C)2C6H4
∫
∫
band containing FcC CC CFc (7 mg, 20%) was also obtained
and identified by comparison with an authentic sample and from
the ES-MS (m/z 418).
(99 mg, 0.374 mmol), and KF (100 mg, 1.72 mmol) in methanol
(40 ml) was heated at reflux for 1 h under a nitrogen atmosphere.
The yellow precipitate formed was collected and washed with
MeOH and hexane and dried to give 13 as a yellow powder
(390 mg, 0.280 mmol, 75%). Anal. Calcd (C78H82P4Ru2): C, 69.53;
H, 6.09; M, 1346. Found: C, 69.17; H, 5.84. IR (Nujol, cm-1):
n(C C) 2067 m, 2046(sh). H NMR (C6D6): d 1.63 (s, 30H, Cp*);
∫
Derivatives of 1,4-(Me3SiC C)2C6F4
∫
(a) 1,4-{Cp(Ph3P)2Ru(C C)}2C6F4 (8). A mixture of 1,4-
1
∫
∫
(Me3SiC C)2C6F4 (24 mg, 0.07 mmol), RuCl(PPh3)2Cp (100 mg,
1.85 (m, 4H, CH2); 2.66 (m, 4H, CH2); 7.02 (m, 16H, meta and para
CH dppe), 7.10 (s, 4H, CH C6H4), 7.12 (m, 8H, meta CH dppe),
7.19 (m, 8H, ortho CH dppe), 7.89 (m, 8H, ortho CH dppe). H
0.14 mol) and KF (8 mg, 0.15 mmol) in thf (5 ml) and MeOH
(20 ml) was heated under reflux for 5 h. The resulting yellow
precipitate was collected and washed with MeOH followed by
1
∫
NMR (CDCl3): d 1.54 (s, 30H, Cp*); 2.05 (m, 4H, CH2); 2.70 (m,
4H, CH2); 6.55 (s, 4H, C6H4), 7.19 (m, 8H, CH dppe), 7.26 (m,
8H, CH dppe), 7.33 (m, 16H, CH dppe), 7.89 (m, 8H, ortho CH
dppe). 31P NMR (C6D6): d 82.1 (s, dppe). 31P NMR (CDCl3): d
82.0 (s, dppe). 13C NMR (C6D6): 10.4 (s, C5Me5), 29.8 (m, CH2),
92.6 (s, C5Me5), 111.5 (s, C∫CC6H4), 129.1, 128.9 (Cp,p¢); 130.4
(CH in C6H4); 133.7, 134.2 (dds, JCP/CCP ~ 5 Hz, Co,o¢); 137.6, 139.7
(m, Ci,i¢). The Cm,m¢ dppe peak is assumed to be hidden by the
C6D6 peak. The low intensity resonances corresponding to Ru–C
and one unique C of C6H4 were not observed. ES-MS (MeOH +
NaOMe, m/z): 1369, [M + Na]+.
hexane to give 1,4-{CpRu(PPh3)2(C C)}2C6F4 (8) (66 mg, 60%).
Anal. Calcd (C92H70P4Ru2F4): C, 70.04; H, 4.47; M, 1578. Found:
C, 70.09; H, 4.47. IR (Nujol, cm-1): n(CC) 2073 m, 2039 m. H
1
NMR (C6D6): d 4.86 (s, 5H, Cp), 6.94–7.75 (m, 30H, Ph). 13C
NMR (CDCl3): d 93.5 (s, Cp), 127.6–137.3 (m, Ph). 19F NMR
(C6D6): d–147.0 (s, C6F4). 31P NMR (C6D6): d 51.7 (s, PPh3). ES-
MS (MeCN, m/z): 1578, M+; 731, [Ru(NCMe)(PPh3)2Cp]+; 691,
[Ru(PPh3)2Cp]+.
∫
(b) 1,4-{Cp(dppe)Ru(C C)}2C6F4 (9). As for 8, 1,4-
∫
(Me3SiC C)2C6F4 (28 mg, 0.08 mmol), RuCl(dppe)Cp (100 mg,
0.17 mmol) and KF (9 mg, 0.16 mmol) in thf (5 ml) and MeOH
∫
(20 ml) gave yellow 1,4-{Cp(dppe)Ru(C C)}2C6F4 (9) (28 mg,
Structure determinations
26%). Anal. Calcd (C72H58P4Ru2F4.CHCl3): C, 60.69; H, 4.12; M
(unsolvated), 1326. Found: C, 60.92; H, 4.11. IR (Nujol, cm-1):
n(CC) 2072 m, 2037 m. 1H NMR (C6D6): d 2.07, 2.70 (2 m,
Full spheres of CCD area-detector diffraction data were measured.
Ntot reflections were merged to N unique (Rint cited) after
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The Royal Society of Chemistry 2008
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©

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“empirical”/multiscan absorption correction (proprietary soft-
ware), No with F > 4s(F) being used in the full matrix least squares
refinements on F2. All data were measured using monochromatic
Bruce, M. G. Humphrey, G. A. Koutsantonis and M. J. Liddell,
J. Organomet. Chem., 1987, 326, 247; (d) M. I. Bruce and M. G.
Humphrey, Aust. J. Chem., 1989, 42, 1067.
7 (a) F. Paul, J.-Y. Mevellec and C. Lapinte, J. Chem. Soc., Dalton Trans.,
2002, 1783; (b) K. Costuas, F. Paul, L. Toupet, J.-F. Halet and C.
Lapinte, Organometallics, 2004, 23, 2053; (c) F. Paul, L. Toupet, J.-Y.
The´pot, K. Costuas, J.-F. Halet and C. Lapinte, Organometallics,
2005, 24, 5464; (d) F. Paul, G. da Costa, A. Bondon, N. Gauthier,
S. Sinbandhit, L. Toupet, K. Costuas, J.-F. Halet and C. Lapinte,
Organometallics, 2007, 26, 874.
8 F. Paul, B. G. Ellis, M. I. Bruce, L. Toupet, T. Roisnel, K. Costuas, J.-F.
Halet and C. Lapinte, Organometallics, 2006, 25, 649.
9 M. A. Fox, R. L. Roberts, W. M. Khairul, F. Hartl and P. J. Low,
J. Organomet. Chem., 2007, 692, 3277.
˚
Mo-Ka radiation, l = 0.71073 A. Anisotropic displacement
parameter forms were refined for the non-hydrogen atoms, (x,
y, z, Uiso)H being included following a riding model. Residuals R,
Rw on F2 are quoted. Neutral atom complex scattering factors
were used; computation used the XTAL 3.7 program system.47
Pertinent results are given in the figures (which show non-hydrogen
atoms with 50% probability amplitude displacement ellipsoids and
˚
hydrogen atoms with arbitrary radii of 0.1 A) and in Tables 1
10 (a) M. I. Bruce, P. J. Low, K. Costuas, J.-F. Halet, S. P. Best and G. A.
Heath, J. Am. Chem. Soc., 2000, 122, 1949; (b) M. I. Bruce, B. D. Kelly,
B. W. Skelton and A. H. White, J. Organomet. Chem., 2000, 604, 150;
(c) M. I. Bruce, B. C. Hall, B. D. Kelly, P. J. Low, M. E. Smith, B. W.
Skelton and A. H. White, J. Chem. Soc., Dalton Trans., 1999, 3719;
(d) M. I. Bruce, B. G. Ellis, P. J. Low, B. W. Skelton and A. H. White,
Organometallics, 2003, 22, 3184; (e) M. I. Bruce, K. Costuas, T. Davin,
B. G. Ellis, J.-F. Halet, C. Lapinte, P. J. Low, M. E. Smith, B. W. Skelton,
L. Toupet and A. H. White, Organometallics, 2005, 24, 3864.
11 F. Coat, P. Thominot and C. Lapinte, J. Organomet. Chem., 2001, 629,
39.
12 (a) M. I. Bruce, M. Ke and P. J. Low, Chem. Commun., 1996, 2405;
(b) M. I. Bruce, M. Ke, P. J. Low, B. W. Skelton and A. H. White,
Organometallics, 1998, 17, 3539.
13 R. Denis, T. Weyland, F. Paul and C. Lapinte, J. Organomet. Chem.,
1997, 545–546, 615.
and 2.
Variata
1. The solvent molecule (benzene) was modelled as disordered
over two sets of sites, occupancy 0.5.
2. xabs refined to -0.07(5); refinement on |F|.
6. Refinement was carried out using the SHELXL 97
program.48
Computations
All DFT computations were carried out with the Gaussian 03
package.49 The model geometries 1-H, 1-F, 8-F and 11-H discussed
here were optimised at the B3LYP/3–21G* level of theory,50
to reduce computational effort, with no symmetry constraints.
Test calculations carried out with a larger basis set gave similar
results, in a manner similar to that reported elsewhere.9 MOs and
frequencies were computed on these optimised geometries at the
same level of theory. All geometries were identified as minima
(no imaginary frequencies). The barriers in the rotations between
the aryl group and the Ru(PH3)2Cp groups in 1-H and 1-F were
estimated by fixing the dihedral angles P1–Ru–C1–C2 at 15◦
intervals (see Fig. 1 for numbering scheme).
14 (a) R. Dembinski, T. Lis, S. Szafert, C. L. Mayne, T. Bartik and J. A.
Gladysz, J. Organomet. Chem., 1999, 578, 229; (b) Q. Zheng and J. A.
Gladysz, J. Am. Chem. Soc., 2005, 127, 10508.
15 (a) A. B. Antonova, M. I. Bruce, B. G. Ellis, M. Gaudio, P. A.
Humphrey, M. Jevric, G. Melino, B. K. Nicholson, G. J. Perkins,
B. W. Skelton, B. Stapleton, A. H. White and N. N. Zaitseva, Chem.
Commun., 2004, 960; (b) A. B. Antonova, M. I. Bruce, P. A. Humphrey,
M. Gaudio, B. K. Nicholson, N. Scoleri, B. W. Skelton, A. H. White
and N. N. Zaitseva, J. Organomet. Chem., 2006, 691, 4694; (c) M. I.
Bruce, M. E. Smith, N. N. Zaitseva, B. W. Skelton and A. H. White,
J. Organomet. Chem., 2003, 670, 170; (d) M. I. Bruce, B. W. Skelton,
A. H. White and N. N. Zaitseva, J. Organomet. Chem., 2003, 683, 398.
16 (a) T. X. Neenan and G. M. Whitesides, J. Org. Chem., 1988, 53, 2489;
(b) P. Nguyen, Z. Yuan, L. Agocs, G. Lesley and T. B. Marder, Inorg.
Chim. Acta, 1994, 220, 289.
17 P. Bladon, D. W. A. Sharp and J. M. Winfield, Spectrochim. Acta, 1964,
20, 1033.
Acknowledgements
18 M. I. Bruce, J. Chem. Soc. A, 1968, 1459.
19 P. G. Pringle and B. L. Shaw, J. Chem. Soc., Dalton Trans., 1983, 889.
20 M. J. Irwin, G. Jia, J. J. Vittal and R. J. Puddephatt, Organometallics,
1996, 15, 5321.
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We thank Professor Brian Nicholson (University of Waikato,
Hamilton, New Zealand) for providing the mass spectra and the
ARC for support of this work and Johnson Matthey plc, Reading,
for a generous loan of RuCl3·nH2O. These studies were facilitated
by travel grants (ARC, Australia; the Royal Society of Chemistry,
UK and the CNRS, France).
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