Syntheses and molecular structures of some polyfluoroaryldiynyl-ruthenium complexes

Article abstract of DOI:10.1016/j.jorganchem.2010.03.017

Lithiated Ru(C{triple bond, long}CC{triple bond, long}CH)(dppe)Cp* reacts with polyfluoroaromatic compounds C₆F₅X (X = F, OMe, CN, NO₂) and C₁₀F₈ to give novel polyfluoroaryldiynyls end-capped with th

Full text of DOI:10.1016/j.jorganchem.2010.03.017

Journal of Organometallic Chemistry 695 (2010) 1561–1568
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Syntheses and molecular structures of some polyfluoroaryldiynyl–ruthenium
complexes
a
b
b
Michael I. Bruce a, , Nancy Scoleri , Brian W. Skelton , Allan H. White
*
a School of Chemistry and Physics, University of Adelaide, Adelaide, South Australia 5005, Australia
b Chemistry M313, SBBCS, University of Western Australia, Crawley, Western Australia 6009, Australia
a r t i c l e i n f o
a b s t r a c t
Article history:
Lithiated Ru(C„CC„CH)(dppe)Cp* reacts with polyfluoroaromatic compounds C6F5X (X = F, OMe, CN,
NO2) and C10F8 to give novel polyfluoroaryldiynyls end-capped with the Ru(dppe)Cp* group. Addition
of tcne to Ru(C„CC„CC6F5)(dppe)Cp* afforded the butadienynyl Ru{C„CC[@C(CN)2]C(C6F5)@C
(CN)2}(dppe)Cp*, while protonation with HBF4ꢀOEt2 resulted in cycloaddition to give [1,3-{Cp*(dppe)
Received 15 February 2010
Received in revised form 11 March 2010
Accepted 11 March 2010
Available online 16 March 2010
RuC„C}2{
l-C4H(C6F5)2}]BF4. XRD molecular structures of complexes with X = F, CN, OMe and the C10F7
derivative are reported.
Keywords:
Ó 2010 Elsevier B.V. All rights reserved.
Alkynyl
Diynyl
Ruthenium
Fluoroaromatic
Crystal structure
1. Introduction
CLi)(PPh3)(NO)Cp* with various metal carbonyls have given
unsaturated carbene complexes {Cp*(Ph3P)(NO)Re}C„CC„CC
A variety of methods is available for the synthesis of diynyl–
metal complexes LnM–C„CC„CR [1]. In general, these depend
upon the availability of the parent diyne HC„CC„CR or its
group 14 derivatives, Me3EC„CC„CR (E = Si, Sn). Most reported
examples involve diynes with R = Me, But, Ph or SiMe3, but con-
temporary interest in poly-ynyl-metal complexes as potential
components in molecular scale electronic devices (wires, switches,
amplifiers) [2–7] suggests that routes to compounds bearing
other functional groups would be useful. The parent diynes often
have limited stability or are difficult to access. However, one po-
tential route which has been little explored is the metallation of
a parent diynyl complex LnMC„CC„CH to give lithio- or magne-
sio-derivatives, which can then be further elaborated. There are
presently relatively few examples of this type of reaction in
the literature. The tungsten diynyl W(C„CC„CH)(CO)3Cp reacts
with LiN(SiMe3)2 to give a derivative which reacted with SiClMe3
or PClPh2 to give W(C„CC„CSiMe3)(CO)3Cp and W{C„CC„
CP(O)Ph2}(CO)3Cp, respectively [8]. Later examples include the
lithiation of Re(C„CC„CH)(PPh3)(NO)Cp* to give Re(C„CC„CLi)
(PPh3)(NO)Cp*, which was then cuprated with CuI or Cu(OBut)
and coupled with IC„CSiMe3 or BrC„CSiEt3 to give Re(C„CC„
CC„CSiR3)(PPh3)(NO)Cp* (R = Me, Et, respectively) [9]; the cop-
per complex has been isolated [10]. Reactions of Re(C„CC„
(OMe)@{MLn} [MLn = Fe(CO)4, Mn(CO)2(g-C5X5) (X5 = HCl4, Cl5, Br5)]
[11].
We have found that metallation of diynyl–ruthenium com-
plexes with organolithium reagents produces synthetically useful
intermediates of the type Ru(C„CC„CLi)(PP)Cp0 [PP = (PPh3)2,
dppe; Cp0 = Cp, Cp*]. For example, addition of LiBu to
Ru(C„CC„CH)(dppe)Cp* in thf solution at ꢁ78 °C, followed by
warming to r.t. to complete the reaction, and cooling again to
ꢁ78 °C before adding an electrophile, has proved to be a useful
route into complexes which are otherwise accessible with diffi-
culty. The reaction of the diynyl-lithium with 1,2-dichlorohexa-
fluorocyclopentene results in displacement of one Cl to give
Ru(C„CC„CC5F6Cl-2)(dppe)Cp* [12].
There is currently some interest in fluorinated aryldi- and poly-
ynes, both from the viewpoint of their solid-state properties [13–
17] and the non-linear optical properties of fluorinated polydiynes
[18]. However, there are relatively few polyfluoroaromatic diynes
known [19,20] and they are not readily employed in the synthesis
of polyfluoroaryl-substituted diynyl complexes. Syntheses are gen-
erally based upon coupling of C6F5I with HC„CSiMe3, followed by
desilylation and Cu(I)-catalysed oxidative coupling to form the
diyne, which can then be further elaborated by conventional nucle-
ophilic substitution reactions [19–21].
Polyfluoroaromatic compounds, exemplified by hexafluoroben-
zene, are characterised by their susceptibility to nucleophilic
attack, in complete contrast to benzene itself [22]. Mono- and
* Corresponding author. Fax: +61 8 8303 4358.
E-mail address: michael.bruce@adelaide.edu.au (M.I. Bruce).
0022-328X/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.03.017

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M.I. Bruce et al. / Journal of Organometallic Chemistry 695 (2010) 1561–1568
di-substitution of ring fluorines by alkynyl groups using LiC„CPh
was first reported in 1967 [23]. This paper describes the syntheses
and characterisation of several diynyl–ruthenium complexes
Ru(C„CC„CArF)(dppe)Cp*, with ArF = C6F5, C6F4OMe-p, C6F4CN-p,
C6F5NO2-p and C10F7-2, and some reactions of the first of these.
pling constants in these spectra. The C6F4X-p (X = OMe, CN, NO2)
compounds 2–4 contained only two equal intensity signals for
the o- and m-F nuclei, again the components of AA0XX0 spin sys-
tems. Assignments are based upon the relative constancy of the
resonances of fluorines adjacent to the dinyl group at dF ca 140.
A NOESY experiment enabled a tentative assignment of the five
resonances observed for 5, based on the XRD structural determina-
tion of this complex as the expected 2-naphthyl isomer. The two
fluorines adjacent to the diynyl group resonate at dF ꢁ150.2 and
ꢁ151.3; resonances at dF ꢁ161.0 and ꢁ163 each have relative
intensity 2 and are assigned to F(4,5) and F(6,7), respectively.
Introduction of the metalladiynyl group does not perturb the
usual substitution reactivity of the fluoroaromatic group, further
reaction of 1 with NaOMe providing an alternative route to 2 in
60% yield. The fluoroaromatic group also does not change the usual
diynyl reactivity. Protonation of 1 gives the binuclear cyclobutenyl-
idinium cation in 6 (Scheme 2) by addition of a putative highly reac-
tive butatrienylidene intermediate to unreacted diynyl. For 6, two
sets of 19F resonances are found, consistent with the structure con-
taining two different C6F5 groups. Although this type of reaction has
been often found between alkynyl and vinylidene complexes [25–
30], there is only one earlier report describing the reaction for diynyl
complexes [31].
The electron-deficient alkene tcne reacts with 1 to give the te-
tracyanobutadienyl complex 7, formed by [2 + 2]-cycloaddition of
the cyanoalkene to the outer C„C triple bond, followed by ring-
opening (Scheme 2). Spectroscopic properties of 7 include the pres-
ence of [M+Na]+ in the ES-MS obtained from solutions containing
NaOMe, and resonances at dC 154.01, 139.14, 92.81 and 78.91 for
the four carbons of the C4 chain. Several examples of this type of
reaction have been described previously [32].
Electrochemical studies (Table 1) showed that the electron-
withdrawing polyfluoroaromatic substituent results in an increase
in the oxidation potential of 1 to +0.56 V when compared with that
of Ru(C„CC„CPh)(dppe)Cp* (+0.44 V), as anticipated when the
more electron-withdrawing C6F5 group replaces Ph. Substitution
of the para-F atom in 1 with OMe results in a reduction of the oxi-
dation potential, two processes occurring here. Irreversible reduc-
tion of the NO2 group in 3 occurs at ꢁ1.45 V, while addition of two
electrons to the tcne adduct 7 gives anionic species which are sta-
bilized by delocalization of charge onto the @C(CN)2 groups. Only 2
and 7 show fully reversible oxidation processes, others being par-
tially reversible under the conditions used.
2. Results and discussion
In general, the ruthenium diynyl complex was lithiated at
ꢁ78 °C and added to a solution of the polyfluoroaromatic com-
pound, also at ꢁ78 °C. After several hours reaction, the product
mixture was worked up after warming to r.t., separation by pre-
parative t.l.c. providing the fluoroaromatic complexes. From these
reactions were obtained Ru(C„CC„CArF)(dppe)Cp* (ArF = C6F5 (1),
C6F4OMe-p (2), C6F4CN-p (3), C6F5NO2-p (4) and C10F7-2 (5);
Scheme 1) in moderate to good yields as yellow to yellow–orange
solids, apparently stable in air indefinitely. Identification of the
products was by elemental microanalyses and from their spectro-
scopic properties. The ES-MS contained molecular ions, together
with the fragment ion [Ru(dppe)Cp*]+ (m/z 635). In all cases, the
Ru(dppe)Cp* moiety was also identified by its characteristic NMR
signals at dH ca 1.55 (Cp*), 2.35 and 3.35 (CH2 of dppe) and Ph mul-
tiplets at dH ca 7.5.
The 13C NMR spectra contained resonances at dC ca 10 and ca 94
(Cp*) and aromatic signals between dC 125 and 135. In some cases,
the carbon chain nuclei were detected. Atom C1 resonates at dC
126.5 for 1 and 5, containing unsubstituted C6F5 or C10F7 groups,
but upfield at dC ca 100 for 2–4. The resonance of atom C2 is found
at dC 99.2 (for 1) or between 92.5 and 95.9 for 2–5. The resonance
for C3 is between dC 89.4 and 90.0 (1, 3–5) but at dC 75.5 for 2, while
C4 resonates at dC 53.3–59.5 (1–3) and 75.5, 76.3 (for 4, 5). At pres-
ent, there is no rationale for these observed differences.
The 19F NMR spectrum of the C6F5 complex 1 contained three
signals at dF ꢁ149.1, ꢁ161.7 and ꢁ166.6 (relative intensities 2/1/
2), assigned to the o-, p- and m-F atoms, respectively. These are
in positions similar to those found in a host of C6F5 compounds
studied some decades ago [24]. The p-F nuclei give rise to triplets
[J(FF) ca 20 Hz] by coupling with the two m-F nuclei; in some cases,
further broadening of the components of the triplet suggests a
smaller unresolved coupling to the o-F nuclei. Signals for the o-
and m-F atoms are multi-line resonances of the AA0XX0 system,
which were not sufficiently resolved for assignment of the cou-
LiBu
H
[Ru*]
Li
[Ru*]
C6F5X
C10F8
[Ru*]
F
F
F
F
F
F
F
1
4
8
F
F
4
3
2
1
2
7
X
Ru
Ph2P
PPh2
6
3
F
5
F
X = F 1, OMe 2, NO2 3, CN 4
5
[Ru*] = Ru(dppe)Cp*
NaOMe
Scheme 1. Syntheses of polyfluoroaromatic diynyl–ruthenium complexes (numbering system for NMR assignments shown).

M.I. Bruce et al. / Journal of Organometallic Chemistry 695 (2010) 1561–1568
1563
C6F5
[Ru*]
1
H+
tcne
(NC)2C
C6F5
H
C6F5
[Ru*]
[Ru*]
+
C(CN)2
C6F5
[Ru*]
7
6
[Ru*] = Ru(dppe)Cp*
Scheme 2. Reactions of Ru(C„CC„CC6F5)(dppe)Cp* with electrophiles.
Table 1
Some electrochemical data for Ru(C„CC„CArF)(dppe)Cp* and derivatives.
afforded the corresponding binuclear cyclobutenylidinium cation,
while tcne adds to the C„C triple bond away from the metal, both
reactions indicating that the diynyl function is not significantly af-
fected by the presence of the fluorinated group.
ArF
Redox potentials/V versus SCE
C6F5 (1)
+0.56a
C6F4OMe-p (2)
C6F4NO2-p (3)
C6F4CN-p (4)
C10F7-2 (5)
+0.17a, +0.34a
ꢁ1.45c, +0.30a, +0.58a
+0.50b
4. Experimental
+0.51a
4.1. General
C6F5-tcne adduct (7)
ꢁ0.89a, ꢁ0.52a, +0.86b
All processes diffusion controlled.
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 argon and degassed before use. Separations were carried
out by preparative thin-layer chromatography on glass plates
(20 ꢂ 20 cm2) coated with silica gel (Merck, 0.5 mm thick).
Conditions: solutions (1 mM) in CH2Cl2 containing 0.1 M [NBu4]PF6 as the sup-
porting electrolyte. CVs were recorded using a PAR Model 263A potentiostat, scan
rate 100 mV sꢁ1. The cell contained Pt-mesh working, Pt wire counter and pseudo-
reference electrodes. Decamethylferrocene was used as an internal reference
(FeCp*2/[FeCp*2]+ = ꢁ0.02 V versus SCE).
a
Partially reversible.
Fully reversible.
Irreversible.
b
c
4.2. Instruments
IR spectra were obtained using a Bruker IFS28 FT-IR spectrom-
eter. Nujol mull spectra were obtained from samples mounted be-
tween NaCl discs. NMR spectra were recorded on a Varian 2000
instrument (1H at 300.145 MHz, 13C at 75.479 MHz, 19F at
282.388 MHz, 31P at 121.501 MHz). Unless otherwise stated, sam-
ples were dissolved in CDCl3 contained in 5 mm sample tubes.
Chemical shifts are given in ppm relative to internal tetramethyl-
silane for 1H and 13C NMR spectra, external H3PO4 for 31P NMR
spectra, and CFCl3 for 19F NMR spectra (referenced to internal
C6F6 at dF ꢁ164.9). Electrospray mass spectra (ES-MS) were ob-
tained from samples dissolved in MeOH which, unless otherwise
stated, contained NaOMe as an aid to ionisation [33]. Solutions
were injected into a Varian Platform II spectrometer via a 10 ml
injection loop. Nitrogen was used as the drying and nebulising
gas. Peaks listed are the most intense of the isotopic clusters. Ele-
mental analyses were by the Campbell Microanalytical Centre, Uni-
versity of Otao, Dunedin, New Zealand.
2.1. Molecular structures
Figs. 1 and 2 depict single molecules of complexes 1, 2, 3 and 4,
selected structural data being collected in Table 2. All contain the
familiar Ru(dppe)Cp* group, with parameters differing little from
many other complexes containing this group, with Ru–P
2.264(1)–2.2824(6) and Ru–C(cp) 2.09(2)–2.37(3) Å and the angles
P(1)–Ru–P(2) 80.09(3)–83.47(4) and P(1,2)–Ru–C(1) 79.8(1)–
91.2(1)°, and having the usual pseudo-octahedral geometry.
The diynyl group is attached to Ru via C(1) [Ru–C(1) range
1.958(2)–1.993(4) Å], with alternating short and long C–C bonds
along the chain [C(1)–C(2) 1.179(5)–1.231(2), C(2)–C(3)
1.361(2)–1.401(6), C(3)–C(4) 1.192(6)–1.212(2), C(4)–C(41)
1.416(2)–1.499(10) Å]. The structures confirm the expected para
substitution of the fluorinated ring, or the 2-substitution of the
naphthyl group. The ring C–F bond lengths are remarkably consis-
tent [(non-disordered) C(4n)–F(4n) 1.314–1.354(3), av.1.34(1) Å].
In the C6 ring of 3, there is an appreciable quinonoid contribution
[1.341, 1.366(2), cf. 1.390–1.404(2) Å], while in the naphthalene
4.3. Reagents
skeleton of 4, the usual Kekulé form persists [four bonds (a–b)
1.344–1.366(4), others 1.407–1.451(4) Å]. In 4, inversion-related
naphthyl groups stack up the centre of the cell along a.
The compound Ru(C„CC„CH)(dppe)Cp* [34] was prepared by
the cited method. Polyfluororomatics were samples supplied by
Imperial Smelting Co., Avonmouth.
3. Conclusions
4.3.1. Ru(C„CC„CC6F5)(dppe)Cp* (1)
A solution of Ru(C„CC„CH)(dppe)Cp* (50 mg, 0.07 mmol) in
Reactions of lithiated Ru(C„CC„CH)(dppe)Cp* with polyfluo-
roaromatic compounds results in substitution of F para to the
substituent, providing a useful route into polyfluoroaryl–diynyl–
ruthenium complexes. Protonation of Ru(C„CC„CC6F5)(dppe)Cp*
THF (10 mL) was treated with BuLi (91
l
L, 1.6 M solution in hex-
ane, 0.145 mmol) and stirred at ꢁ78 °C for 30 min. C6F6 (17
lL,
0.14 mmol) was then added and the reaction was stirred at
ꢁ78 °C for 1 h before being allowed to warm to r.t. over 3 h.

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M.I. Bruce et al. / Journal of Organometallic Chemistry 695 (2010) 1561–1568
Fig. 1. Plots of molecules of (a) Ru(C„CC„CC6F5)(dppe)Cp* (1) (major component) and (b) Ru(C„CC„CC6F4OMe-p)(dppe)Cp* (2).
Solvent was then removed to give a residue which was dissolved in
hexane (90 mL) and the solution was filtered via cannula and evap-
orated to dryness to give Ru(C„CC„CC6F5)(dppe)Cp* 1 as an or-
ange powder (50 mg, 80%). Alternatively, the hexane extract was
chromatographed (basic Al2O3 column; hexane-CH2Cl2-NEt3, 16/
3/1) to give a bright yellow fraction containing pure 1. Single crys-
tals suitable for X-ray studies were grown from CH2Cl2/hexane.
Anal. Calc. (C46H39F5P2Ru): C, 64.93; H, 4.62; M, 850. Found: C,
2J(CP) 2 Hz, C5Me5]; 89.37 (s, C3); 53.27 (s, C4); 29.85 (m, CH2CH2);
10.05 (s, C5Me5). 19F NMR (C6D6): d ꢁ149.1 (m, 2F, o-F); ꢁ161.7 [t,
3J(FF) = 22 Hz, 1F, p-F]; ꢁ166.6 (m, 2F, m-F). 31P NMR (C6D6): d 80.8
(s, dppe). ES-MS (positive ion, MeOH, m/z): 1702, [2M]+; 851, M+;
635, [Ru(dppe)Cp*]+.
4.3.2. Ru(C„CC„CC6F4OMe-p)(dppe)Cp* (2)
64.72; H, 4.90%. IR/cmꢁ1
: m(C„C) 2151m, 2005m; m(CF) 1513m,
(a) Similarly, the reaction of Ru(C„CC„CH)(dppe)Cp* (50 mg,
0.07 mmol) with nBuLi (91
lL, 1.6 M solution in hexane,
1488m, 1434m, 1376m, 1261m, 1093m, 1060m, 981m, 805m,
741m, 693m. 1H NMR (C6D6): d 7.42–7.01 (m, 20H, Ph); 2.47,
1.79 (2m, 2 ꢂ 2H, PCH2); 1.56 (s, 15H, Cp*). 13C NMR (C6D6): d
134.48–127.75 (m, Ph); 126.48 (s, C1); 99.23 (s, C2); 93.80 [t,
0.145 mmol), followed by addition of C6F5OMe (21 L, 0.14 mmol)
l
afforded Ru(C„CC„CC6F4OMe-p)(dppe)Cp* 2 as an orange pow-
der (38 mg, 60%).

M.I. Bruce et al. / Journal of Organometallic Chemistry 695 (2010) 1561–1568
1565
Fig. 2. Plots of molecules of (a) Ru(C„CC„CC6F4CN-p)(dppe)Cp* (3) and (b) Ru(C„CC„CC10F7-2)(dppe)Cp* (4).
(b) Ru(C„CC„CC6F5)(dppe)Cp* (31 mg, 0.04 mmol) was dis-
solved in thf (10 mL) and NaOMe (1.2 mg in 2 mL of MeOH,
0.05 mmol) was added. The solution was stirred at r.t. for 16 h.
The solvent was removed and the residue was dissolved in hexane
(60 mL) and then evaporated to dryness to afford 2 as an orange
powder (27 mg, 87%). Single crystals suitable for X-ray studies
were grown from CH2Cl2/hexane. Anal. Calc. for C47H42F4OP2Ru:
29.87 (m, CH2CH2); 10.08 (s, C5Me5). 19F NMR (C6D6): d ꢁ142.5
(m, 2F); ꢁ161.6 (m, 2F). 31P NMR (C6D6): d 80.8 (s, dppe). ES-MS
(+ve ion, MeOH, m/z): 862, M+; 885, [M+Na]+; 635, [Ru(dppe)Cp*]+.
4.3.3. Ru(C„CC„CC6F4NO2-p)(dppe)Cp* (3)
Similarly, from Ru(C„CC„CH)(dppe)Cp* (50 mg, 0.07 mmol)
and C6F5NO2 (30 lL, 0.14 mmol) was obtained Ru(C„CC„CC6F4-
C, 65.42; H, 4.91; M, 862. Found: C, 65.39; H, 5.03%. IR/cmꢁ1
(C„C) 2149m, 2005m; (CO) 1711m; (CF) 1573m, 1501m,
:
NO2-p)(dppe)Cp* 3 as a purple powder (52 mg, 80%). Anal. Calc.
m
m
m
for C46H39F4NO2P2Ru: C, 63.01; H, 4.48; N, 1.60; M, 878. Found:
1480m, 1434m, 1377m, 1263m, 1095m, 1026m, 804m, 742m,
698m. 1H NMR (C6D6): d 7.37–7.02 (m, 20H, Ph); 3.30 (s, 3H,
OCH3); 2.46–1.77 (2m, 2 ꢂ 2H, PCH2); 1.54 (s, 15H, Cp*). 13C
NMR (C6D6): d 136.78–127.64 (m, Ph); 100.28 (s, C1); 93.71 (s,
C5Me5); 92.54 (s, C2); 89.95 (s, C3); 74.00 (s, OCH3); 53.26 (s, C4);
C, 63.07; H, 4.52, N, 1.63%. IR/cmꢁ1
: m(C„C) 2126m, 1998m;
m
(NO) 1634m; m(CF) 1556m, 1504m, 1455m, 1435m, 1259m,
1016m, 802m, 767m, 697m. 1H NMR (C6D6): d 7.42–7.04 (m,
20H, Ph); 2.35, 1.83 (2m, 2 ꢂ 2H, PCH2); 1.56 (s, 15H, Cp*). 13C
NMR (C6D6): d 133.77–126.44 (m, Ph); 100.25 (s, C1); 94.26 [t,

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M.I. Bruce et al. / Journal of Organometallic Chemistry 695 (2010) 1561–1568
Table 2
Selected bond parameters.
Bond
1
2 (mols 1; 2)
3
4
Bond distances (Å)
Ru–P(1)
Ru–P(2)
Ru–C(cp)
(av.)
Ru–C(1)
2.2797(10)
2.2712(10)
2.09–2.33(2); 2.24–2.37(3)
2.20(13); 2.29(6)
1.993(4)
2.269(1); 2.264(1)
2.281(1); 2.276(1)
2.241–2.278(4), 2.223–2.266(4)
2.26; 2.25(2)
2.2656(6)
2.2754(9)
2.229–2.290(2)
2.27(3)
2.2689(6)
2.2824(6)
2.232–2.272(2)
2.256(16)
1.976(2)
1.991(4); 1.976(4)
1.958(2)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(41)
C(4n)–F(4n)
1.179(5)
1.402(6)
1.197(5)
1.431(9); 1.44(2)
1.309–1.344(10) [< >1.335(16)];
1.31(2)–1.386(14) [< >1.35(3)]
1.226(5); 1.219(6)
1.373(6); 1.370(7)
1.206(5); 1.192(6)
1.499(10); 1.495(11)
1.291–1.379(9), 1.335–1.388(10); 1.257–1.408(12), 1.200–
1.408(10) [< >1.34(4), 1.36(2); 1.36(7), 1.34(10)]
1.231(2)
1.361(2)
1.212(2)
1.416(2)
1.340–1.345(2)
[< >1.342(2)]
1.209(3)
1.373(3)
1.199(3)
1.421(3)
1.314–1.354(3)
[< >1.338(14)]
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(3)
C(2)–C(3)–C(4)
C(3)–C(4)–C(41)
83.30(4)
83.9(1)
86.8(1)
174.9(3)
171.2(4)
178.5(5)
166.9(6); 175.0(8)
83.47(4); 83.20(4)
79.8(1); 83.2(1)
91.2(1); 87.2(1)
173.8(3); 174.5(4)
176.1(4); 173.6(5)
179.7(5); 177.8(6)
175.7(6); 163.5(7)
80.09(3)
86.07(5)
85.71(6)
171.9(1)
168.1(2)
178.2(2)
167.4(2)
83.32(2)
80.53(6)
87.13(6)
178.7(2)
174.3(2)
178.2(3)
173.5(3)
For 1: values are given for the two disordered components.
For 2: C(44)–O(44) 1.421(7), 1.387(10) Å.
For 3: C(44)–C(441) 1.434(2), C(441)–N(441) 1.141(2) Å; C(44)–C(441)–N(441) 178.2(2)°.
2J(CP) 2 Hz, C5Me5]; 94.40 (s, C2); 89.38 (s, C3); 76.28 (s, C4); 31.89
(m, CH2CH2); 10.22 (s, C5Me5). 19F NMR (C6D6): d ꢁ140.3 (m, 2F);
ꢁ151.9 (m, 2F). 31P NMR (C6D6): d 80.4 (s, dppe). ES-MS (positive
ion, MeOH + NaOMe, m/z): 901, [M+Na]+; 878, M+; 635,
[Ru(dppe)Cp*]+.
4.3.6. [1,3-{Cp*(dppe)RuC„C}2{
To solution of Ru(C„CC„CC6F5)(dppe)Cp* (31 mg,
L, 0.04 mmol)
and the mixture was stirred at r.t. for 16 h. The solvent was re-
moved and the blue residue was dissolved in minimum amount
of CH2Cl2 and was added to hexane with rapid stirring. The result-
ing precipitate was collected on a sintered funnel and washed
l-C4H(C6F5)2-2,4}]BF4 (6)
a
0.04 mmol) in THF (15 mL) was added HBF4ꢀOEt2 (6
l
4.3.4. Ru(C„CC„CC6F4CN-p)(dppe)Cp* (4)
with hexane to afford [1,3-{Cp*(dppe)RuC„C}2{
BF4 as bright blue powder (23 mg, 84%). Anal. Calc.
(C92H79BF14P4Ru2): C, 61.73; H, 4.45; M (cation), 1699. Found: C,
61.50; H, 4.38%. IR/cmꢁ1
(CH) 2924m, (C„C) 1965m, 1897m;
(CF) 1573m, 1500m, 1435m, 1397m, 1264m, 1158m, 1089m,
l-C4H(C6F5)2-2,4}]
Similarly, the reaction of Ru(C„CC„CH)(dppe)Cp* (50 mg,
6
a
0.07 mmol) with BuLi (0.17 mL, 0.86 M solution in hexane,
0.145 mmol) and C6F5CN (19 L, 0.14 mmol) gave Ru(C„CC„
l
:
m
m
CC6F4CN-p)(dppe)Cp* 4 as an orange powder (58 mg, 90%). Single
crystals suitable for X-ray studies were grown from benzene/hex-
ane. Anal. Calc. for C47H39F4NP2Ru: C, 65.80; H, 4.59; N, 1.63; M,
m
876m, 746m, 697m. 1H NMR (C6D6): d 7.42–6.89 (m, 40H, Ph);
2.14, 2.11 (2m, 2 ꢂ 4H, PCH2); 2.02 (s, 1H, H); 1.70 (s, 30H, Cp*).
13C NMR (CDCl3): d 320.72 (s, C1); 201.55 (s, C2); 132.59–127.36
(m, Ph); 116.7 (s, C3); 102.07 (s, C4); 97.77 (s, C5Me5); 29.37 (m,
CH2CH2); 9.27 (s, C5Me5). 19F NMR (CDCl3): d -158.1 (m, 2F, m-F);
ꢁ164.0 (m, 2F, m-F); ꢁ176.9 [t, 3J(FF) = 22 Hz, 1F, p-F]; ꢁ172.3 [t,
3J(FF) = 22 Hz, 1F, p-F]; ꢁ184.0 (m, 2F, o-F); ꢁ185.5 (m, 2F, o-F).
31P NMR (C6D6): d 81.0 (s, dppe). ES-MS (MeOH, m/z): 1700,
[MꢁH]+; 635, [Ru(dppe)Cp*]+.
857. Found: C, 65.70; H, 4.61, N, 1.63%. IR/cmꢁ1
:
m
(CN) 2214m;
m(C„C) 2128m, 1995m; m(CF) 1634m, 1486m, 1435m, 1380m,
1264m, 1095m, 978m, 803m, 743m, 698m. 1H NMR (C6D6): d
7.27–7.06 (m, 20H, Ph); 2.53, 1.98 (2m, 2 ꢂ 2H, PCH2); 1.53 (s,
15H, Cp*). 13C NMR (C6D6): d 133.68–127.63 (m, Ph); 99.39 (s,
C1); 94.75 (s, C2); 94.25 (s, C5Me5); 75.49 (s, C3); 59.48 (s, C4);
31.95 (m, CH2CH2); 10.01 (s, C5Me5). 19F NMR (C6D6): d ꢁ138.7
(m, 2F); ꢁ139.3 (m, 2F). 31P NMR (C6D6): d 80.2 (s, dppe). ES-MS
(positive ion, MeOH, m/z): 858, [M+H]+; 635, [Ru(dppe)Cp*]+.
4.3.7. Ru{C„CC[@C(CN)2]C(C6F5)@C(CN)2}(dppe)Cp* (7)
4.3.5. Ru(C„CC„CC10F7-2)(dppe)Cp* (5)
To
a
suspension of Ru(C„CC„CC6F5)(dppe)Cp* (31 mg,
Similarly, from Ru(C„CC„CH)(dppe)Cp* (50 mg, 0.07 mmol)
and C10F8 (22 mg, 0.07 mmol) was obtained Ru(C„CC„CC10F7-
2)(dppe)Cp* 5 as an orange powder (24 mg, 35%). Anal. Calc. for
C50H39F7P2Ru: C, 64.17; H, 4.20. Found: C, 64.19; H, 4.19%. IR
0.04 mmol) in benzene (15 mL) was added TCNE (5 mg,
0.04 mmol) resulting in an immediate colour change from yellow
to green. The mixture was stirred at r.t for 7 h. The solvent was re-
moved and the residue was extracted in minimum CH2Cl2 and
purified by preparative t.l.c. plates using 1:1 CH2Cl2/Et2O as eluant
cmꢁ1/:
m(C„C) 2138m, 2008m; m(CF) 1651m, 1574m, 1470m,
1455m, 1403m, 1263m, 1197m, 1095m, 1026m, 949m, 805m,
744m, 697m. 1H NMR (C6D6): d 7.54–6.89 (m, 20H, Ph); 2.62,
1.78 (2m, 2 ꢂ 2H, PCH2CH2P); 1.56 (s, 15H, Cp*). 13C NMR (C6D6):
d 133.94–127.75 (m, Ph); 126.56 (s, C1); 95.93 (s, C2); 94.06 [t,
2J(CP) 2 Hz, C5Me5]; 89.49 (s, C3); 75.48 (s, C4); 30.25 (m, CH2CH2);
10.17 (s, C5Me5). 19F NMR (C6D6): d ꢁ150.2 [t, 3J(FF) = 19 Hz, 1F],
ꢁ151.3 [t, 3J(FF) = 20 Hz, 1F], ꢁ157.3 [dt, 3J(FF) = 18 Hz,
to give a green band containing Ru{C„CC[@C(CN)2]C(C6F5)@
C(CN)2}(dppe)Cp* 7 (41 mg, 97%). Anal. Calc. for C52H39F5N4P2Ru:
C, 63.79; H, 4.02; N, 5.73. Found: C, 63.43; H, 4.51; N, 5.41%. IR/
cmꢁ1):
m(CN) 2211m; m(C„C) 1964m; m(CF) 1573m, 1521m,
1455m, 1262m, 1096m, 966m, 802m, 743m, 697m. 1H NMR
(CDCl3): d 7.45–7.15 (m, 20H, Ph); 2.78, 2.23 (2m, 2 ꢂ 2H, PCH2);
1.53 (s, 15H, Cp*). 13C NMR (CDCl3): d 154.01 (s, C1); 139.14 (s,
C2); 132.88–128.29 (m, Ph); 116.53, 116.33 (2 ꢂ s, 2 ꢂ CN);
111.30, 110.62 (2 ꢂ s, 2 ꢂ CN); 92.81 (s, C3); 97.37 [t, 2J(CP) 2 Hz,
C5Me5]; 78.91 (s, C4); 29.99 (m, CH2CH2); 9.95 (s, C5Me5). 19F
NMR (CDCl3): d ꢁ159.8 (m, 2F, m-F); ꢁ168.9 [t, 3J(FF) = 22 Hz, 1F,
4
4J(FF) = 8 Hz, 1F], ꢁ161.0 [dt, 3J(FF) = 18 Hz, J(FF) = 58 Hz, 1F],
ꢁ163.0 [dt, 3J(FF) = 18 Hz, 4J(FF) = 65 Hz, 1F]. 31P NMR (C6D6): d
80.7 (s, dppe). ES-MS (+ve ion, MeOH, m/z): 937, M+; 969,
[M+MeOH]+; 635, [Ru(dppe)Cp*]+.

M.I. Bruce et al. / Journal of Organometallic Chemistry 695 (2010) 1561–1568
1567
Table 3
Crystal data and refinement details.
Complex
1
2
3
4
Formula
MW
C46H39F5P2Ru
849.83
C47H42F4OP2Ru
861.82
C47H39F4NP2Ru.C6H6
934.91
C50H39F7P2Ru
935.82
Crystal system
Space group
monoclinic
C2/c
triclinic
triclinic
triclinic
P1
P1
P1
a (Å)
b (Å)
c (Å)
29.275(2)
15.0289(10)
22.2046(10)
11.653(1)
12.314(1)
29.680(5)
100.29(1)
93.22(1)
105.582(7)
4012
13.011(3)
13.059(3)
15.493(2)
106.22(1)
91.64(3)
119.58(2)
2154
10.0040(3)
12.4220(5)
18.1524(6)
85.737(3)
79.806(3)
69.074(3)
2074
a
(°)
b (°)
127.934(8)
c
(°)
V (Å3)
7705
qc
1.465
1.427
1.441
1.499
Z
l
8
0.55
4
0.53
2
0.49
2
0.52
(Mo K
a
) (mmꢁ1
)
Tmin/max
0.89
0.97
0.97
0.72
Crystal dimensions (mm3)
0.32 ꢂ 0.10 ꢂ 0.07
0.32 ꢂ 0.21 ꢂ 0.08
0.28 ꢂ 0.15 ꢂ 0.14
0.23 ꢂ 0.14 ꢂ 0.065
2hmax (°)
57
63
63
69
Ntot
N (Rint
No
43789
8963 (0.071)
4018
123031
25526 (0.074)
10374
67484
13861 (0.040)
10029
43907
16507 (0.048)
9601
)
R1
0.044
0.060
0.031
0.045
wR2 (a)
0.100 (0.049)
0.166 (0.078)
0.074 (0.040)
0.096 (0.042)
p-F]; ꢁ179.8 (m, 2F, o-F). 31P NMR (CDCl3): d 81.1 (s, dppe). ES-MS
(MeOH+NaOMe, m/z): 1001, [M+Na]+; 635, [Ru(dppe)Cp*]+.
Appendix A. Supplementary material
CCDC 687428, 687429, 687430, 687431 contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplementary
data associated with this article can be found, in the online version,
at doi:10.1016/j.jorganchem.2010.03.017.
4.4. Structure determinations
Full spheres of diffraction data were measured at ca 100 K using
a CCD area-detector instrument. Ntot reflections were merged to N
unique (Rint cited) after ‘‘empirical”/multiscan absorption correc-
tion (proprietary software), No with F > 4
‘‘observed”. All data were measured using monochromatic Mo K
r(F) being considered
References
a
radiation, k = 0.71073 Å. In the full-matrix least squares refine-
[1] P.J. Low, M.I. Bruce, Adv. Organomet. Chem. 48 (2001) 71.
[2] (a) F. Paul, C. Lapinte, Coord. Chem. Rev. 178–180 (1998) 427;
(b) F. Paul, C. Lapinte, in: M. Gielen, R. Willem, B. Wrackmeyer (Eds.), Unusual
Structures and Physical Properties in Organometallic Chemistry, Wiley,
Chichester, 2002, p. 220.
[3] R.L. Carroll, C.B. Gorman, Angew. Chem., Int. Ed. Engl. 41 (2002) 4379.
[4] N. Robertson, G.A. McGowan, Chem. Soc. Rev. 32 (2003) 96.
[5] N.J. Long, C.K. Williams, Angew. Chem., Int. Ed. Engl. 42 (2003) 2586.
[6] P.J. Low, Dalton Trans. (2005) 2821.
[7] S. Rigaut, D. Touchard, P.H. Dixneuf, in: T. Hirao (Ed.), Redox Systems under
Nano-space Control, Springer, Heidelberg, 2006.
[8] M.I. Bruce, M. Ke, P.J. Low, B.W. Skelton, A.H. White, Organometallics 17 (1998)
3539.
ments on F2, anisotropic displacement parameter forms were re-
fined for the non-hydrogen atoms, (x, y, z, Uiso)H being included
following a riding model. Neutral atom complex scattering factors
were used; computation used the SHELXL 97 program [35] [weights:
(r
2(F2) + (aP)2)ꢁ1 (P = (Fo2 + 2Fc2)/3)]. Pertinent results are given in
the figures (which show non-hydrogen atoms with 50% probability
amplitude displacement envelopes and hydrogen atoms with arbi-
trary radii of 0.1 Å, as well as numbering schemes) and in Tables 2
and 3).
[9] R. Dembinski, T. Lis, S. Szafert, C.L. Mayne, T. Bartik, J.A. Gladysz, J. Organomet.
Chem. 578 (1999) 229.
[10] R. Dembinski, T. Bartik, B. Bartik, M. Jaeger, J.A. Gladysz, J. Am. Chem. Soc. 122
(2000) 810.
4.5. Variata
[11] T. Bartik, W. Weng, J.A. Ramsden, S. Szafert, S.B. Falloon, A.M. Arif, J.A. Gladysz,
J. Am. Chem. Soc. 120 (1998) 11071.
[12] M.I. Bruce, A.M. Burgun, C.R. Parker, B.W. Skelton, J. Organomet. Chem. 695
(2010) 619.
[13] S. Okada, H. Matsuda, M. Otsuka, H. Nakanishi, M. Kato, Bull. Chem. Soc. Jpn. 67
(1994) 483.
[14] B.-Q. Chen, J.-X. Wen, Cryst. Liq. Cryst. Sci. Technol. A: Mol. Cryst. Liq. Cryst.
289 (1996) 141.
[15] G.W. Coates, A.R. Dunn, L.M. Henling, D.A. Dougherty, R.H. Grubbs, Angew.
Chem., Int. Ed. Engl. 36 (1997) 248.
[16] M. Gdaniec, W. Jankowski, M.J. Milewska, T. Polonski, Angew. Chem., Int. Ed.
42 (2003) 3903.
[17] L. Shu, Z. Mu, H. Fuchs, L. Chi, M. Mayor, Chem. Commun. (2006) 1862.
[18] (a) S. Okada, H. Matsuda, H. Nakanishi, M. Kato, M. Otsuka, J. Photopolym. Sci.
Tehnol. 1 (1988) 354;
1. All aromatic substituents (including Cp*) were modelled as
disordered over pairs of sites, occupancies set at 0.5 after trial
refinement for the Cp* component, 0.757(3) and complement for
the pendants of P(1) and 0.685(3) and complement for the pen-
dants of P(2) and the fluoroaromatic group.
2. In both molecules of the asymmetric unit, the C6F4O and CH3
groups were modelled as disordered over two sets of sites, occu-
pancies set at 0.5 after trial refinement. The disorder detracts from
the definition of the OMe groups and their assignment rests on the
chemistry.
(b) S. Okada, H. Matsuda, H. Nakanishi, M. Kato, M. Otsuka, Thin Solid Films
179 (1989) 423;
(c) S. Okada, H. Nakanishi, H. Matsuzawa, H. Katagi, T. Oshikiri, H. Kasai, A.
Sarkar, H. Oikawa, R. Rangel-Rojo, T. Fukuda, H. Matsuda, in: Proc. SPIE, 3796,
Org. NLO Materials, p. 76.
Acknowledgements
We thank the Australian Research Council for support of this
work and Johnson Matthey plc (Reading, UK) for a generous loan
of RuCl3ꢀnH2O.
[19] R.R. Tykwinski, J. Kendall, R. McDonald, Synlett (2009) 2068.
[20] (a) O.M. Abu Salah, M.I. Bruce, Aust. J. Chem. 29 (1976) 531.;
(b) O.M. Abu Salah, M.I. Bruce, Aust. J. Chem. 30 (1977) 2639.

1568
M.I. Bruce et al. / Journal of Organometallic Chemistry 695 (2010) 1561–1568
[21] (a) Y. Zhang, J. Wen, Synthesis (1990) 727;
[30] R.F. Winter, Eur. J. Inorg. Chem. (1999) 2121.
(b) Y. Zhang, J. Wen, W. Du, J. Fluorine Chem. 49 (1990) 293;
(c) Y. Zhang, J. Wen, J. Fluorine Chem. 51 (1991) 75, 229, 433.;
(d) Y. Zhang, Y. Hu, J. Wen, J. Fluorine Chem. 58 (1992) 111.
[22] (a) R.D. Chambers, Fluorine in Organic Chemistry, Wiley, Chichester, 1973. p.
261;
(b) R.D. Chambers, R.H. Mobbs, Adv. Fluorine Chem. 4 (1965) 50.
[23] M.R. Wiles, A.G. Massey, Tetrahedron Lett. 8 (1967) 5137.
[24] (a) M.I. Bruce, J. Chem. Soc. A (1968) 1459;
[31] M.I. Bruce, B.G. Ellis, B.W. Skelton, A.H. White, J. Organomet. Chem. 690 (2005)
1772.
[32] (a) M.I. Bruce, M. Ke, P.J. Low, B.W. Skelton, A.H. White, Organometallics 17
(1998) 3539;
(b) M.I. Bruce, M.E. Smith, B.W. Skelton, A.H. White, J. Organomet. Chem. 484
(2001) 637–639.;
(c) M.I. Bruce, P.J. Low, M. Ke, B.D. Kelly, B.W. Skelton, M.E. Smith, A.H. White,
N.B. Witton, Aust. J. Chem. 54 (2001) 453;
(b) M.I. Bruce, J. Organomet. Chem. 21 (1970) 415.
[25] N.E. Kolobova, V.V. Skripkin, G.G. Aleksandrov, Yu.T. Struchkov, J. Organomet.
Chem. 169 (1979) 293.
[26] R.M. Bullock, J. Am. Chem. Soc. 109 (1987) 8087.
[27] B.E. Boland-Lussier, R.P. Hughes, Organometallics 1 (1982) 635.
[28] W. Weng, T. Bartik, M.T. Johnson, A.M. Arif, J.A. Gladysz, Organometallics 14
(1995) 889.
[29] (a) H. Fischer, F. Leroux, G. Roth, R. Stumpf, Organometallics 15 (1996) 3723;
(b) F. Leroux, R. Stumpf, H. Fischer, Eur. J. Inorg. Chem. (1998) 1225.
(d) M.I. Bruce, F. de Montigny, M. Jevric, C. Lapinte, B.W. Skelton, M.E. Smith,
A.H. White, J. Organomet. Chem. 689 (2004) 2860;
(e) M.I. Bruce, M. Jevric, C.R. Parker, W. Patalinghug, B.W. Skelton, A.H. White,
N.N. Zaitseva, J. Organomet. Chem. 693 (2008) 2915.
[33] W. Henderson, J.S. McIndoe, B.K. Nicholson, P.J. Dyson, J. Chem. Soc., Dalton
Trans. (1998) 519.
[34] M.I. Bruce, B.G. Ellis, M. Gaudio, C. Lapinte, G. Melino, F. Paul, B.W. Skelton,
M.E. Smith, L. Toupet, A.H. White, Dalton Trans. (2004) 1601.
[35] G.M. Sheldrick, Acta Crystallogr., Sect. A64 (2008) 112.