Iodo-alkynyl- and iodo-butadiynyl-ruthenium complexes

Article abstract of DOI:10.1016/j.jorganchem.2008.06.008

Addition of [I(py)₂]BF₄ to Ru(C{triple bond, long}CH)(dppe)Cp* gave the iodovinylidene [Ru({double bond, long}C{double bond, long}CHI)(dppe)Cp*]BF₄ 1, which could be deprotonated to Ru(C{triple bond, long}CI)(dppe)Cp* 2. T

Full text of DOI:10.1016/j.jorganchem.2008.06.008

Journal of Organometallic Chemistry 693 (2008) 2915–2920
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Iodo-alkynyl- and iodo-butadiynyl-ruthenium complexes
a
a
b,1
Michael I. Bruce a, , Martyn Jevric , Christian R. Parker , Wyona Patalinghug
,
*
Brian W. Skelton b, Allan H. White b, Natasha N. Zaitseva a
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:
Addition of [I(py)2]BF4 to Ru(C„CH)(dppe)Cp gave the iodovinylidene [Ru(@C@CHI)(dppe)Cp ]BF4 1,
*
*
Received 22 April 2008
Received in revised form 4 June 2008
Accepted 4 June 2008
which could be deprotonated to Ru(C„CI)(dppe)Cp 2. The attempted preparation of Ru(C„C
*
C„CI)(dppe)Cp , followed by derivatisation with tcne, gave the dienynyl Ru{C„CC[@C(CN)2]-
*
CI@C(CN)2}(dppe)Cp 3. The Pd(0)/Cu(I)-catalysed reaction of 3 with Ru{C„CC„CAu(PPh3)}(dppe)Cp
*
*
Available online 11 June 2008
afforded Ru{C„CC@C(CN)2C@C(CN)2Au(PPh3)}(dppe)Cp 4 by formal replacement of I+ by [Au(PPh3)]+.
*
XRD structures of 1–4 are reported.
Keywords:
Ó 2008 Elsevier B.V. All rights reserved.
Ruthenium
Tetracyanoethene
XRD structure
Diynyl
Iodo-alkynyl
Gold
1. Introduction
numerous occasions with organic halo-alkenes or –alkynes [13],
we considered that a desirable target would be the reverse reaction
Iodo-di- and poly-ynes have developed into useful reagents for
a variety of syntheses, ranging from linear carbon allotropes [1]
through ordered poly(diiodobutadiyne) [2] to a variety of highly
unsaturated organic molecules including natural products [3].
Considerable interest has been evinced in their spectroscopic
properties [4], while their formulation as iodine-capped carbon
chains renders them also suitable for molecular assembly [5].
in which iodo-alkynyl- or -poly-ynyl-metal complexes could be
employed. There appear to be relatively few iodo-alkynyl-metal
complexes described, of which recent examples are Ru(C„CI)-
L2(g
5-C9H7) [L2 = (PPh3)2, dppe], obtained from the corresponding
lithiated ethynyl complexes and [I(py)2]BF4 [14]. Hitherto, our
experience has been that iodoethynyl-metal complexes are some-
what unstable and do not readily lend themselves to isolation and
further characterisation. However, by using the bulky and elec-
Metal complexes have included systems such as {MLn}2(
IC2C2I) (MLn = WCl5 [6], Rh2( -O2CCF3)4(OCMe2) [7]), and iododiy-
l- : -
g2 g2
l
tron-rich Ru(dppe)Cp fragment as an end-group, we have been
*
nes have been employed in the Cadiot–Chodkiewicz reaction [8].
Several hypervalent iodonium derivatives are known [9]. The
syntheses of bis(carbene) complexes via iododiynes such as
IC„CC„CSiMe3 has been reported [10], while thermolysis within
molecular sieves such as MCM-41 results in polymerisation to
form novel oligo-ynes [11].
More recently, we described a methodology towards long car-
bon chains end-capped by transition metal groups which involves
elimination of phosphine–gold(I) halides between compounds
containing C(sp)– or C(sp2)–X bonds and alkynyl or poly-ynyl-
gold(I) complexes [12]. While we have used this approach on
able to synthesise Ru(C„CI)(dppe)Cp , and to obtain evidence for
*
the formation of the next homologue, Ru(C„CC„CI)(dppe)Cp .
*
2. Results and discussion
We sought to prepare an iodoethynyl complex from the reac-
tion between Ru(C„CH)(dppe)Cp and [I(py)2]BF4. However, the
*
only product obtained was the iodovinylidene [Ru(@C@CHI)-
(dppe)Cp ]BF4 1 (Scheme 1). This complex was identified by micro-
*
analysis and from its ES-MS, which contained M+ and [MÀI]+ at m/z
787 and 660, respectively. In the IR spectrum, there was no m(C„C)
band, but a medium intensity band at 1612 cmÀ1 can be assigned
to
(C@C). In the 1H NMR spectrum, the vinylidene proton is found
* Corresponding author. Fax: +61 8 8303 4358.
E-mail addresses: mbruce@chemistry.adelaide.edu.au, michael.bruce@adelaide.
edu.au (M.I. Bruce).
m
at d 4.62, while the characteristic downfield triplet C resonance at
a
1
dC 323.94 also lends support to the structural interpretation.
On leave from the Department of Chemistry, De La Salle University, Taft Avenue,
1004 Manila, The Phillipines.
Confirmation of the nature of this compound was achieved by a
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.06.008

2916
M.I. Bruce et al. / Journal of Organometallic Chemistry 693 (2008) 2915–2920
BF4
I
[I(py)2]BF4
NaOMe
Ru
C
C
Ru
C
C
I
Ru
C
C
H
Ph2P
Ph2P
Ph2P
H
PPh2
PPh2
PPh2
1
2
Scheme 1.
single-crystal XRD structure determination. Addition of positive io-
dine to the Ru–C„CH fragment to give Ru@C@CHI+ follows the
precedent established many years ago in the reaction of
Ru(C„CPh)(PPh3)2Cp with I2 [19].
version, although the identity of a second pink product also formed
is presently unknown. Addition of tcne to transition metal alkynyl
complexes often proceeds through a radical intermediate [18],
although in the present case we were not able to observe this inde-
pendently, the reaction mixture becoming dark green within five
minutes and changing to the deep purple colour of the major prod-
uct after 30 min. It is presumed that the first-formed adduct is the
cyclobutenyl complex, often observed in related reactions, but that
this undergoes a rapid ring-opening reaction to afford the isolated
complex.
The isolation of the tcne adduct is reasonable evidence that the
iododiynyl-ruthenium complex is formed and further experiments
were designed to explore the chemistry of this unusual species. In
the first of these, we considered whether the iodo complex 3 would
undergo loss of phosphine–gold(I) iodide in a Pd(0)/Cu(I)-catalysed
Treatment of 1 with base (KOBut) resulted in ready deprotona-
tion to afford orange Ru(C„CI)(dppe)Cp 2 in 86% yield, character-
*
ised by microanalysis and spectroscopic methods, together with a
single-crystal XRD structure determination. A strong m(C„C) band
is found at 1995 cmÀ1, while the NMR spectra contained the reso-
nances characteristic of the Ru(dppe)Cp group. In addition, a sin-
*
a
glet at dC À13.42 could be assigned to C , but the resonance of Cb
was not distinguishable. In the ES-MS, notable ions included
[2(MÀI)+Na]+ and [2(MÀI)]+ at m/z 1341 and 1318, respectively.
Lithiation of Ru(C„CC„CH)(dppe)Cp readily affords a deriva-
*
tive which can be considered to be Ru(C„CC„CLi)(dppe)Cp ,
*
although it is unlikely that the molecular structure is as simple
as this representation implies. Similar lithio-poly-ynyl complexes
have also been described by Wong [15], Akita [16] and Gladysz
[17]. When the lithio derivative was made in situ, followed by
addition of [I(py)2]BF4 at À78 °C, a yellow solution was obtained.
Several attempts to isolate the supposed iodobutadiynyl complex
were unsuccessful, but addition of the electrophilic alkene tcne re-
sulted in a rapid colour change to dark purple. Separation by pre-
parative t.l.c. (silica gel, acetone–dichloromethane, 1/99) afforded
two products, of which the major component 3 formed dark purple
crystals. The minor product has not yet been fully characterised.
Compound 3 was characterised as the tetracyanoiodobutadie-
reaction with Ru{C„CC„CAu(PPh3)}(dppe)Cp . Somewhat to our
*
surprise, we found instead that the orange-red product was formed
by replacement of the I atom in 3 with a Au(PPh3) group, i.e.,
Ru{C„CC@C(CN)2C@C(CN)2Au(PPh3)}(dppe)Cp
4 (61% yield).
*
The fate of the ‘Ru(C4)(dppe)Cp ’ fragment could not be deter-
*
mined: possibly it was contained in the extensive dark baseline
(perhaps formed by oxidation) observed during the t.l.c. purifica-
tion of 4. Complex 4 was also obtained from a conventional addi-
tion of tcne to Ru{C„CC„CAu(PPh3)}(dppe)Cp (41% yield). The
*
molecular formula was established by microanalysis and from its
ES-MS (M+ at m/z 1270), and the molecular structure was deter-
mined from a single-crystal XRD study. The spectroscopic proper-
nyl complex Ru{C„CC[@C(CN)2]CI@C(CN)2}(dppe)Cp by means
ties were consistent with this structure, with
m
m(CN) at 2207,
*
of elemental analyses and a single-crystal XRD study (see below).
The spectroscopic properties were in accord with the solid-state
(C„C) at 1980 and v(C@C) at 1440 cmÀ1. The Ru(dppe)Cp group
*
showed the usual resonances [Cp at dH 1.53, dC 10.23 and 96.22;
*
structure, including
m
m
(CN) at 2206 and 2188 cmÀ1, and a broad
dppe at dH 2.14, 2.96 and between 7.12 and 7.57, dC 29.87 (CH2),
multiple aromatic signals between dC 127.87–134.74 (Ph), and dP
40.3 (PPh3), 80.3, 81.0 (AB q, dppe)]. While four singlets between
dC 111.8–117.33 can be assigned to the CN groups, only one carbon
chain signal can be assigned, at dC 121.18.
(C„C) band at 1965 cmÀ1. The 1H NMR spectrum contained reso-
nances for Cp (d 1.25), dppe-CH2 (d 1.97–2.06 and 2.53–2.62) and
*
Ph protons (d 6.78–7.25). The 13C NMR spectrum contains reso-
nances at d 10.01 and 97.32 (Cp ), 29.30–29.91 (dppe CH2), four
*
singlets between d 110.44 and 115.77 (CN) and multiple aromatic
signals between d 127.97 and 133.56. The skeletal carbons of the C4
chain were found at d 98.62, 134.24–136.46 and 144.71. The dppe
31P nuclei formed an AB quartet at d 80.3 and 80.7 [J(PP) = 17 Hz].
The EI-MS, from a solution in MeOH and MeCN containing NaOMe,
contained a strong ion at m/z 961, assigned to [M+Na]+, together
with weak M+ and [MÀI]+. Unusually, at higher m/z, ions corre-
sponding to [2M+Na]+ (m/z 1899) suggest that some association
occurs in solution. The redox properties include an irreversible
wave at À0.78 V [assigned to reduction of the @C(CN)2 groups]
and two oxidation processes at +0.86 and +1.28 V, occurring at
the Ru–Cn chain.
Molecular structures: Characterisation of the four complexes 1–4
was achieved by single-crystal XRD studies (Figs. 1–4, Table 1). To
our knowledge, 2 is the first structurally characterised complex
containing an iodoethynyl group, which has the normal parame-
ters Ru–C 2.007(3), C(1)–C(2) 1.196(4) and C(2)–I 2.022(3) Å, with
angles at C(1) and C(2) of 176.5(3) and 168.3(3)°. The organic li-
gand in 3 is confirmed as the tetracyanoiodobutadienylethynyl
group, with C(1)–C(2) 1.241(6), C(2)–C(3) 1.375(5), C(3)–C(30)
1.393(7), C(3)–C(4) 1.484(3), C(4)–C(40) 1.342(5) Å (< >, all mole-
cules, both solvates). Angles at atoms C(1, 2) are 170.6–176.1(4)°
as expected for the C„C triple bond, while those around C(3, 4)
range between 115.2° and 125.9(3)°, with torsion angles C(30)–
C(3)–C(4)–C(40) À69.0(5) to À78.5(5)°, consistent with their being
C(sp2) atoms with the s-trans configuration found in previous
examples of this type of complex. These values can be compared
with values found in somewhat related compounds
(NC)2C@C6H2I2@C(CN)2, which has C@C(CN)2, CI@CH and C–I
bonds of 1.388, 1.356 and 2.080(2) Å [20], and ButC6H4C„C-
The chemistry described above is summarised in Scheme 2.
Metallation of Ru(C„CC„CH)(dppe)Cp with LiBu affords the
*
lithio derivative, which is iodinated at the terminal carbon using
[I(py)2]BF4 as reported earlier for Ru(C„CLi)(PPh3)2(g
5-C9H7)
[14]. By keeping the mixture at low temperatures, we were able
to perform the subsequent reaction with tcne in reasonable con-

M.I. Bruce et al. / Journal of Organometallic Chemistry 693 (2008) 2915–2920
2917
1) BuLi
2) [I(py)2]BF4
Ru
C
C
C
C
X
Ru
C
C
C
C
I
thf/ -78oC
X = H
Ph2P
Ph2P
PPh2
PPh2
X = SiMe3
AuCl(PPh3) / NaOMe
X = Au(PPh3)
tcne
tcne
CN
C
CN
C
NC
NC
C
Ru{(C2C2Au(PPh3)}
(dppe)Cp*
C
Au(PPh3)
CN
I
Ru
C
C
C
Ru
PPh2
C
C
C
Pd(0) / Cu(I)
Ph2P
Ph2P
C
C
CN
PPh2
NC
NC
4
3
Scheme 2.
Fig. 1. Projection of the cation in [Ru(@C@CHI)(dppe)Cp]BF4 (1).
Fig. 2. Projection of a molecule of Ru(C„CI)(dppe)Cp (2).
*
CI@CIC6H4But, which has C„C, C(sp)@C(sp2), C@CI and C–I of
1.208(7), 1.427(9), 1.317(9) and 2.111, 2.123(7) Å, respectively,
[21].
these distances are longer, at 2.3123, 2.3314(4) Å. The lengthening
may be ascribed to reduction in back-bonding from Ru to P, caused
by either or both of the presence of the positive charge on the
metal centre and the strongly electron-accepting vinylidene ligand.
Similarly, the Ru–C(cp) distances are longer in 1, although the
unusually wide range of these distances (ca. 0.1 Å) masks the
difference. Note that in all of 1–4, the shorter Ru–C(cp) distances
lie, in projection, in the vicinity of the unsaturated substituent.
In 2, the Ru–C(1) and C(1)–C(2) distances are 2.007(3) and
1.196(4) Å, respectively, in the normal range for Ru–C(sp) and
C„C triple bonds. However, in 3 and 4, these distances are shorter
[Ru–C(1) 1.921(7) 3 (< >), 1.945(2) Å 4] and longer [C(1)–C(2)
1.241(6) 3 (< >), 1.235(3) Å 4], which suggests a relatively large
contribution from the allenylidene tautomer. In the three iodine-
containing compounds, the C–I distances range between 2.022(3)
[C(sp)–I] and 2.108(2) Å [C(sp2)–I]. The considerable bending at
C(2) in 4 [167.4(2)°, 167.0(2)°] probably results from intramolecu-
lar interactions between phenyl groups.
3. Conclusions
The Ru(dppe)Cp groups have pseudo-octahedral geometry, the
This work has described the preparation and isolation of the
*
structural parameters being similar to those found in many other
related complexes. In the neutral complexes 2–4, Ru–P separations
range between 2.2544(7) and 2.3028(7) Å, while in the cation of 1,
iodoethynyl complex Ru(C„CI)(dppe)Cp
2 by reaction of
*
[I(py)2]BF4 to Ru(C„CH)(dppe)Cp to give the iodovinylidene com-
*
plex [Ru(@C@CHI)(dppe)Cp ]BF4 1, followed by deprotonation
*

2918
M.I. Bruce et al. / Journal of Organometallic Chemistry 693 (2008) 2915–2920
Pt-mesh working electrode, Pt wire counter and pseudo-reference
electrodes; scan rate 100 mV sÀ1. Samples (1 mM) were dissolved
in CH2Cl2 containing 0.1 M [NBu4]PF6 as the supporting electrolyte.
Potentials are given in V vs SCE, determined using ferrocene as
internal calibrant (FeCp2/[FeCp2]+ = +0.46 V). Elemental analyses
were by CMAS, Belmont, Vic., Australia.
4.2. Reagents
Ru(C„CH)(dppe)Cp [23], Ru(C„CC„CX)(dppe)Cp [X = H,
*
*
SiMe3, Au(PPh3)] [22] and [I(py)2]BF4 [24] were made as previously
described.
4.2.1. [Ru(@C@CHI)(dppe)Cp ]BF4
1
*
To a solution of Ru(C„CH)(dppe)Cp (150 mg, 0.227 mmol) in
*
CH2Cl2 (10 mL) was added [I(py)2][BF4] (89 mg, 0.239 mmol) and
the stirred solution was protected from light. The solution turned
from yellow to dark green and after 30 min, half the solvent was
removed under reduced pressure and hexane (20 mL) was layered
on top of the solution. After 1 d the crude product was collected
and recrystallised (CH2Cl2/hexane) to give dark orange crystals of
Fig. 3. Projection of a molecule of Ru{C„CC[@C(CN)2]CI@C(CN)2}(dppe)Cp (3).
[Ru(@C@CHI)(dppe)Cp ]BF4 1 (141 mg, 71%). X-ray quality crystals
*
were grown from (acetone/hexane). Anal. Calc. (C38H40BF4IN2Ru):
C, 52.25; H, 4.62; M (cation), 787. Found: C, 51.95; H, 4.76%. IR (Nu-
jol, cmÀ1): (BF) 1052s (br). 1H NMR (acetone-d6): d
m(C@C) 1612s, m
1.74 (s, 15H, Cp ), 2.81, 3.02 (2 Â m, 2 Â CH2, dppe), 4.62 (s, 1H,
*
C@CH), 7.12–7.24, 7.59–7.82 (m, 20H, Ph), 13C NMR (acetone-d6):
d 10.43 (C5Me5), 103.56 (s, @CH), 104.86 (s, C5Me5), 128.94–
134.92 (m, Ph), 323.94 [t, J(CP) = 16 Hz, Ru@C]. 31P NMR (ace-
tone-d6): d 74.6 [s, 2P, Ru(dppe)]. ES-MS (MeOH, m/z): 635, [Ru(dp-
pe)Cp ]+; 660, [MÀI]+; 787, M+.
*
4.2.2. Ru(C„CI)(dppe)Cp 2
*
A solution of [Ru(@C@CHI)(dppe)Cp ]BF4 (50 mg, 0.057 mmol)
*
in CH2Cl2 (8 mL) was treated with KOBut (8 mg, 0.063 mmol) and
the mixture was stirred for 30 min. Solvent was removed, the res-
idue taken up in CH2Cl2, filtered and evaporated, and extracted
with benzene–hexanes (1/3). Evaporation of the filtered solution
afforded yellow Ru(C„CI)(dppe)Cp 2 (38 mg, 86%). X-ray quality
*
crystals were obtained from benzene–hexanes. Anal. Calc.
(C38H39IP2Ru): C, 58.09; H, 5.00; M, 786. Found: C, 60.03; H,
5.33%. IR (CH2Cl2, cmÀ1): (C„C) 1995s. 1H NMR (C6D6): d 1.59
m
(s, 15H, Cp ), 1.85, 2.55 (2 Â m, 2 Â CH2, dppe), 7.03–7.31, 7.80–
*
Fig. 4. Projection of a molecule of Ru{C„CC[@C(CN)2]C[Au(PPh3)]@C(CN)2}(dp-
pe)Cp (4).
7.86 (m, 20H, Ph). 13C NMR (C6D6): d -13.42 (s, CI), 10.68 (C5Me5),
29.71–30.31 (m, CH2P), 93.15 (s, C5Me5), 127.85–139.85 (m, Ph).
31P NMR (C6D6): d 81.9 (s, 2P, dppe). ES-MS (positive ion mode,
MeOH + NaOMe, m/z): 1341, [2(MÀI)+Na]+; 1318, [2(MÀI)]+; 786,
with NaOMe. The putative preparation of Ru(C„CC„CI)(dppe)Cp ,
*
M+; 659, [MÀI]+; 635, [Ru(dppe)Cp ]+.
derivatised with tcne to give the dienynyl Ru{C„CC[@C(CN)2]-
*
CI@C(CN)2}(dppe)Cp 3, is also reported. A Pd(0)/Cu(I)-catalysed
*
reaction of 1 with afforded Ru{C„CC„CAu(PPh3)}(dppe)Cp 4 by
4.2.3. Ru{C„CC[@C(CN)2]CI@C(CN)2}(dppe)Cp 3
*
*
formal replacement of I+ by [Au(PPh3)]+.
LiBu (0.10 mL, 2.5 M solution in hexanes, 0.25 mmol) was added
to a soluton of Ru(C„CC„CH)(dppe)Cp (156 mg, 0.23 mmol) in
*
4. Experimental
THF (10 mL) at À78 °C. After stirring the mixture for 5 min,
[I(py)2]BF4 (88 mg, 0.24 mmol) was added and stirring was contin-
ued for a further 20 min. Addition of tcne (33 mg, 0.26 mmol) at
À78 °C was followed by warming the reaction mixture to r.t. Re-
moval of solvent under vacuum and purification by preparative
t.l.c. (silica gel, acetone–dichloromethane, 1/99) afforded a dark
4.1. 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 Â 20
cm2) coated with silica gel (Merck, 0.5 mm thick). Spectroscopic
and electrochemical data were acquired using instrumentation
which is fully described elsewhere [13]; unless otherwise stated,
NMR spectra were measured on CDCl3 solutions. Electrochemistry
was carried out with a 263 potentiostat, using a cell containing a
purple band containing Ru{C„CC[@C(CN)2]CI@C(CN)2}(dppe)Cp
*
3 (99 mg, 46%), together with a pink fraction containing as yet
unidentified material (20 mg). Crystals for the XRD studies were
obtained from Et2O/hexane or from benzene/hexane. Anal. Calc.
for C46H39IN4P2Ru: C, 58.92; H, 4.19; N, 5.97; M, 938. Found: C,
59.01; H, 4.23; N, 5.93%. IR (Nujol, cmÀ1):
m
(CN) 2206m, 2188w;
m
(C„C) 1965s (br), 1545w, 695m. 1H NMR: d 1.25 (s, 15H, Cp ),
*
1.97–2.06, 2.53–2.62 (2 Â m, 2 Â 2H, PCH2), 6.78–7.25 (m, 20H,

M.I. Bruce et al. / Journal of Organometallic Chemistry 693 (2008) 2915–2920
2919
Ph). 13C NMR: d 10.01 (s, C5Me5), 29.3–29.9 (m, CH2), 97.32
(C5Me5), 98.62, 144.71 (2 Â s, C@C), 110.44, 113.80, 115.71,
115.77 (4 Â s, CN), 127.97–128.47, 129.66–130.55, 132.11–
132.47, 132.94–133.56 (4 Â m, Ph), 134.24–136.46 (m), 144.71
(C@C). 31P NMR: d 80.3, 80.9 [AB q, J(PP) = 17 Hz]. ES-MS (MeOH +
MeCN + NaOMe, m/z): 1899, [2M+Na]+; 961, [M+Na]+; 811, [MÀI]+.
Electrochemistry: À0.78 (rev.), +0.86, +1.28 V (quasi-rev.).
Ru{C„CC@C(CN)2C@C(CN)2Au(PPh3)}(dppe)Cp 4 (14 mg, 61%),
*
isolated as
P3Ru + 0.5CH2Cl2): C, 59.07; H, 4.19; N, 4.27; M, 1270. Found: C,
59.24; H, 4.30; N, 5.3%. IR (CH2Cl2, cmÀ1):
(CN) 2207, (C„C)
1980vs,
a
dark red solid. Anal. Calc. (C64H54AuN4-
m
m
m
(C@C) 1440m. 1H NMR: d 1.53 (s, 15H, Cp ), 2.14, 2.96
*
(2 Â m, 2 Â CH2, dppe), 7.12–7.57 (m, 35H, Ph). 13C NMR: d 10.23
(C5Me5), 29.87 (m, PCH2), 96.22 (s, C5Me5), 111.81, 116.61,
116.91, 117.33 (4 Â s, CN), 121.18 (s, C) 127.87–134.74 (m, Ph).
31P NMR: d 40.3 (s, 1P, AuPPh3), 80.3, 81.0 [AB q, J(PP) = 15 Hz,
4.2.4. Ru{C„CC@C(CN)2C@C(CN)2Au(PPh3)}(dppe)Cp 4
*
(a) To a mixture of Ru{C„CC@C(CN)2C@C(CN)2I}(dppe)Cp
2P, Ru(dppe)]. ES-MS (MeOH/NaOMe, m/z): 635, [Ru(dppe)Cp ]+;
*
*
(17 mg, 0.018 mmol), Ru{C„CC„CAu(PPh3)}(dppe)Cp (21 mg,
1270, M+; 1293, [M+Na]+.
*
0.018 mmol), CuI (1 mg, 0.005 mmol) and Pd(PPh3)4 (4 mg,
0.004 mmol) was added THF (8 mL). The whole was stirred at r.t.
for 2 h. Solvent was removed and the residue taken up in CH2Cl2
and purified by column chromatography (flash silica, CH2Cl2–hex-
ane, 3:1). The major orange red fraction contained
(b) A solution of Ru{C„CC„CAu(PPh3)}(dppe)Cp (35 mg,
*
0.031 mmol) and tcne (8 mg, 0.062 mmol) in benzene (6 mL) was
stirred at r.t. overnight to give a burgundy-red solution containing
some red-orange precipitate. The latter was removed by filtration,
washed with benzene, and the combined filtrates were evaporated.
Table 1
Selected bond parameters
Complex
1
2
3 Á C6H6 (molecule 1)
4 (molecule 1)
Bond distances (Å)
Ru–P(1,2)
<Ru–C(cp)>
Range
2.3123(4), 2.3314(4)
2.29(5)
2.242(1)–2.340(1)
1.840(1)
2.2544(7), 2.2743(7)
2.25(2)
2.211–2.266(3)
2.007(3)
2.2950(7), 2.2846(7)
2.27(2)
2.237–2.298(3)
1.921(3)
2.2614(5), 2.2750(5)
2.26(3)
2.228(2)–2.293(2)
1.945(2)
Ru–C(1)
C(1)–C(2)
C(2)–C(3)
C(3)–C(30)
C(3)–C(4)
C(4)–C(40)
C(4)–X
1.312(2)
1.196(4)
1.246(4)
1.373(4)
1.401(4)
1.488(4)
1.348(4)
2.079(3) [I]
1.235(3)
1.392(3)
1.392(3) [C(31)]
1.478(3)
1.352(3) [C(41)]
2.037(2) [Au]
2.108(2) [C(2), I]
2.022(3) [C(2), I]
Bond angles (°)
P(1)–Ru–P(2)
82.18(1)
83.48(3)
83.47(2)
82.40(2)
P(1,2)–Ru–C(1)
Ru–C(1)–C(2)
85.19(5), 93.09(5)
172.7(1)
84.81(8), 83.88(8)
176.5(3)
84.96(7), 86.18(7)
174.2(2)
84.26(6), 88.45(6)
174.5(2)
C(1)–C(2)–C(3)
C(2)–C(3)–C(30, 4)
C(4)–C(3)–C(30)
C(3)–C(4)–C(40)
C(3,40)–C(4)–X
175.1(3)
125.5(2), 116.1(2)
118.4(2)
121.8(2)
115.3(2), 122.9(2) [I]
167.4(2)
124.1(2), 116.7(2) [C(31)]
119.0(2) [C(31)]
119.2 (2) [C(41)]
126.9(2) [C(41), Au]
118.7(1) [C(1)–C(2)–I]
168.3(3) [C(1)–C(2)–I]
For 4: Au–P(3) 2.2801(6) Å; C(4)–Au–P(3) 170.56(6)°.
Table 2
Crystal data and refinement details
Complex
1 Á 0.5C6H14
2
3 Á 0.5Et2O
3 Á 0.5C6H6
4 Á 0.5CH2Cl2
Formula
MW
C38H40IP2Ru+ Á BF4À Á 0.5C6H14
C38H39IP2Ru
785.60
C46H39IN4P2Ru Á 0.5C4H10
O
C46H39IN4P2Ru Á 0.5C6H6
C64H54AuN4P3Ru Á 0.5CH2Cl2
916.51
974.78
976.78
1312.52
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Triclinic
P1
Monoclinic
P21/n
10.2764(2)
22.7746(4)
14.8638(3)
Triclinic
P1
Triclinic
P1
Triclinic
P1
ꢀ
ꢀ
ꢀ
ꢀ
12.6322(3)
13.0458(3)
13.8756(3)
74.163(2)
73.837(2)
61.872(2)
1910
15.786(2)
16.885(2)
17.620(2)
100.297(3)
102.623(3)
99.801(3)
4401
15.706(2)
16.891(2)
17.669(2)
100.360(2)
102.755(2)
98.698(2)
4407
14.9285(2)
18.6541(2)
21.2289(2)
82.111(1)
85.412(1)
74.736(1)
5643
a
(°)
b (°)
109.469(2)
c
(°)
V (Å3)
3280
1.591
4
qc (g cmÀ3
Z
)
1.594
2
1.471
4
1.472
4
1.545
4
2hmax/deg.
80
1.35
68
1.54
66
1.17
66
1.17
72
3.04
l(MoK
a
) (mmÀ1
)
Tmin/max
0.86
0.94
0.90
0.84
0.77
Crystal dimensions (mm3)
0.48 Â 0.42 Â 0.37
0.36 Â 0.18 Â 0.03
0.45 Â 0.42 Â 0.31
0.55 Â 0.48 Â 0.42
0.36 Â 0.28 Â 0.25
208826
51040 (0.032)
37912
Ntot
89091
62072
59067
59196
N (Rint
)
23327 (0.024)
17373
13225 (0.065)
9166
31102 (0.033)
19182
31118 (0.027)
22869
No
R1
0.035
0.043
0.052
0.044
0.028
wR2 (a, b)
S
0.105 (0.055, 0.86)
1.11
0.114 (0.061, À)
0.14 (0.07, 1.07)
1.05
0.12 (0.06, 2.29)
1.08
0.076 (0.03, 2.90)
1.09
0.95
T (K)
100
100
153
153
100

2920
M.I. Bruce et al. / Journal of Organometallic Chemistry 693 (2008) 2915–2920
[3] (a) A. Sorg, K. Siegel, R. Bruckner, Chem. Eur. J. 11 (2005) 1610;
(b) K. Siegel, R. Bruckner, Chem. Eur. J. 4 (1998) 1116.
[4] (a) J.P. Maier, O. Marthaler, E. Kloster-Jensen, J. Electr. Spectrosc. Relat.
Phenom. 18 (1980) 251;
Purification of a CH2Cl2 extract of the residue by preparative t.l.c.
(acetone-hexane, 3/7) gave major burgundy-red band
(Rf = 0.33) which contained Ru{C„CC@C(CN)2C@C(CN)2Au(PPh3)}-
a
(b) M. Allan, E. Kloster-Jensen, J.P. Maier, O. Marthaler, J. Electr. Spectrosc.
Relat. Phenom. 14 (1978) 359;
(c) P. Klaboe, E. Kloster-Jensen, E. Bjarnov, D.H. Christensen, O.F. Nielsen,
Spectrochim. Acta A 31A (1975) 931;
(dppe)Cp 4 (16 mg, 41%), obtained as red crystals (CH2Cl2/
hexane).
*
(d) A. Rogstad, L. Benestad, S.J. Cyvin, J. Mol. Struct. 23 (1974) 265;
(e) M.K. Phibbs, Spectrochim. Acta A 29 (1973) 599.
4.3. Structure determinations
[5] K. Gao, N.S. Goroff, J. Am. Chem. Soc. 122 (2000) 9320.
[6] K. Stahl, K. Dehnicke, J. Organomet. Chem. 316 (1986) 85.
[7] E.V. Dikarev, N.S. Goroff, M.A. Petrukhina, J. Organomet. Chem. 683 (2003) 337.
[8] B.N. Ghose, D.R.M. Walton, Synthesis (1974) 890.
[9] (a) P.J. Stang, R. Tykwinski, J. Am. Chem. Soc. 114 (1992) 4411;
(b) P.J. Stang, J. Ullmann, Synthesis (1991) 1073;
(c) P.J. Stang, V.V. Zhdankin, J. Am. Chem. Soc. 112 (1990) 6437.
[10] (a) C. Hartbaum, H. Fischer, J. Organomet. Chem. 578 (1999) 186;
(b) C. Hartbaum, E. Mauz, G. Roth, K. Weissenbach, H. Fischer, Organometallics
18 (1999) 2619.
[11] J. Hlavaty, J. Rathousky, A. Zukal, L. Kavan, Carbon 39 (2000) 53.
[12] 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, A.H. White, N.N. Zaitseva,
Chem. Commun. (2004) 960.
[13] (a) A.B. Antonova, M.I. Bruce, P.A. Humphrey, M. Gaudio, B.K. Nicholson, N.
Scoleri, B.W. Skelton, A.H. White, N.N. Zaitseva, J. Organomet. Chem. 691
(2006) 4694;
Full spheres of diffraction data were measured using a CCD
area-detector instrument. Ntot reflections were merged to N unique
(Rint cited) after ‘‘empirical”/multiscan absorption correction
(proprietary software), No with F>4r(F) considered ‘‘observed”.
All data were measured using monochromatic Mo K
a radiation,
k = 0.71073 Å. In the full matrix least squares refinements on F2,
anisotropic displacement parameter forms were refined for the
non-hydrogen atoms, (x, y, z, Uiso H
‘‘riding” model [reflection weights: (
)
being included following a
r
2(F2) + (aP)2 + (bP))À1
,
P = (F2o + 2F2c)/3]. Neutral atom complex scattering factors were used
within the SHELXL 97 program [25]. Pertinent results are given in
the figures (which show non-hydrogen atoms with 50% probability
amplitude displacement ellipsoids) and Tables 1 and 2.
(b) M.I. Bruce, M.L. Cole, M. Gaudio, B.W. Skelton, A.H. White, J. Organomet.
Chem. 691 (2006) 4601;
(c) M.I. Bruce, B.W. Skelton, A.H. White, N.N. Zaitseva, Organometallics 25
(2006) 4817;
(d) M.I. Bruce, N.N. Zaitseva, P.J. Low, B.W. Skelton, A.H. White, J. Organomet.
Chem. 691 (2006) 4273;
(e) M.I. Bruce, N.N. Zaitseva, B.W. Skelton, J. Organomet. Chem. 691 (2006)
759;
(f) M.I. Bruce, P.A. Humphrey, G. Melino, B.W. Skelton, A.H. White, N.N.
Zaitseva, Inorg. Chim. Acta 358 (2005) 1453;
4.3.1. Variata
In the benzene solvate of 3, the solvent was modelled as
disordered over two sets of sites, occupancies 0.5. In both (isomor-
phous) solvates there are weak interactions from the I atoms of one
molecule to C(n31) of the other [I(1)ÁÁÁC(231) (1 À x, y, 1 À z)
2.969(4), 3.010(3); I(2)ÁÁÁC(131) (1 À x, 1 À y, 1 À z) 2.958(4),
2.974(3) Å (Et2O, C6H6 solvates).
(g) M.I. Bruce, B.W. Skelton, A.H. White, N.N. Zaitseva, J. Organomet. Chem.
683 (2003) 398;
(h) M.I. Bruce, M.E. Smith, N.N. Zaitseva, B.W. Skelton, A.H. White, J.
Organomet. Chem. 670 (2003) 170.
Acknowledgements
[14] M.P. Gamasa, J. Gimeno, I. Godefroy, E. Lastra, B.M. Martín-Vaca, S. García-
Granda, A. Gutierrez-Rodriguez, J. Chem. Soc., Dalton Trans. (1995) 1901.
[15] A. Wong, P.C.W. Kang, C.D. Tagge, D.R. Leon, Organometallics 9 (1990) 1992.
[16] M. Akita, M.-C. Chung, A. Sakurai, S. Sugimoto, M. Terada, M. Tanaka, Y. Moro-oka,
Organometallics 16 (1997) 4882.
We thank Professor Brian Nicholson (University of Waikato,
Hamilton, New Zealand) for providing the mass spectra, the ARC
for support of this work and Johnson Matthey plc, Reading, for a
generous loan of RuCl3 Á nH2O.
[17] R. Dembinski, T. Bartik, B. Bartik, J.A. Gladysz, J. Am. Chem. Soc. 122 (2000)
810.
[18] (a) M.I. Bruce, T.W. Hambley, M.R. Snow, A.G. Swincer, Organometallics 4
(1985) 494;
(b) M.I. Bruce, T.W. Hambley, M.R. Snow, A.G. Swincer, Organometallics 4
(1985) 501.
[19] M.I. Bruce, G.A. Koutsantonis, M.J. Liddell, B.K. Nicholson, J. Organomet. Chem.
320 (1987) 217.
[20] J.S. Miller, J.C. Calabrese, R.L. Harlow, D.A. Dixon, J.H. Zhang, W.M. Rieff,
S. Chittipeddi, M.A. Selover, A.J. Epstein, J. Am. Chem. Soc. 112 (1990) 5496.
[21] J. Barluenga, I. Llorente, L.J. Alvarez-Garcia, J.M. Gonzalez, P.J. Campos, M.R.
Diaz, S. Garcia-Granda, J. Am. Chem. Soc. 119 (1997) 6933.
[22] 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.
[23] M.I. Bruce, B.G. Ellis, P.J. Low, B.W. Skelton, A.H. White, Organometallics 22
(2001) 3184.
Appendix A. Supplementary material
CCDC 667568, 667569, 667739, 667740 and 690141 contain the
supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplemen-
tary data associated with this article can be found, in the online
version, at doi:10.1016/j.jorganchem.2008.06.008.
References
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A Program for Crystal Structure Refinement,
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