Syntheses and structural studies of several diynyl-ruthenium complexes and their adducts with cyano-alkenes

Article abstract of DOI:10.1002/zaac.201100123

Herein are described some continuing investigations into the reactions of cyano-alkenes with diynyl-ruthenium complexes which have resulted in the preparation and characterisation of diynyl-ruthenium compounds Ru(C≡CC≡CR)(PP)Cp [R = Ph, PP = dppe; R = Fc, PP = dppf; R = CPh=CBr₂, PP = (PPh₃)₂], together with the polycyanobutadienyls Ru{C≡CC[=C(CN)₂]CR=CR′(CN)}(PP) Cp′ [R = Fc, (PP)Cp′ = (dppf)Cp; R = H, SiMe₃, (PP)Cp′ = (dppe)Cp*] formed by [2 + 2]-cycloaddition of the cyano-alkenes to the outer C≡C triple bonds and subsequent ring-opening reactions. Single-crystal XRD molecular structure determinations of six complexes are reported. Copyright

Full text of DOI:10.1002/zaac.201100123

ARTICLE
DOI: 10.1002/zaac.201100123
Syntheses and Structural Studies of Several Diynyl-Ruthenium Complexes
and their Adducts with Cyano-Alkenes
Michael I. Bruce,*[a] Alexandre Burgun,[a] Guillaume Grelaud,[a] Martyn Jevric,[a]
Brian K. Nicholson,[b] Brian W. Skelton,[c] Allan H. White,[c] and Natasha N. Zaitseva[a]
Keywords: Ruthenium; Diinyl; Cyanocarbon; X-ray diffraction; Alkenes
Abstract. Herein are described some continuing investigations into the obutadienyls Ru{C≡CC[=C(CN)2]CR=CR'(CN)}(PP)Cp' [R
= Fc,
reactions of cyano-alkenes with diynyl-ruthenium complexes which (PP)Cp' = (dppf)Cp; R = H, SiMe3, (PP)Cp' = (dppe)Cp*] formed by
have resulted in the preparation and characterisation of diynyl-ruthe- [2 + 2]-cycloaddition of the cyano-alkenes to the outer C≡C triple
nium compounds Ru(C≡CC≡CR)(PP)Cp [R = Ph, PP = dppe; R = Fc, bonds and subsequent ring-opening reactions. Single-crystal XRD mo-
PP = dppf; R = CPh=CBr2, PP = (PPh3)2], together with the polycyan- lecular structure determinations of six complexes are reported.
In order to further enhance our understanding of this chemis-
Introduction
try, we have prepared further examples of related diynyl- and
Over the past couple of decades, we have described the ex-
polycyanobutadienyl- ruthenium complexes. The syntheses
tensive chemistry of poly-ynyl-ruthenium complexes contain-
and characterisation of six complexes and their X-ray deter-
ing the Ru(PP)Cp' [PP = (PPh3)2, Cp' = Cp; PP = dppe, Cp' =
mined-structures are reported below.
Cp, Cp*] end-groups.[1] One point of interest has been the re-
actions of diynyl complexes with electrophilic alkenes, such as
tetracyanoethene (tcne). These reactions proceed by initial [2
+ 2]-cycloaddition to give (often unobserved) cyclobutenes
which then undergo rapid ring-opening to form tetracyanobuta-
dienes (Scheme 1).[2] The site of addition is often the outer
Results
Syntheses and Properties
Most compounds described herein have been characterised
(from the metal atom) C≡C triple bond, although in one in- by elemental microanalyses and from their spectroscopic prop-
stance we have obtained two isomers of the adduct from tcne erties, including IR and NMR spectroscopy and electro-spray
and Ru(C≡CC≡CFc)(dppe)Cp, namely Ru{C[=C(CN)2]C[= mass spectrometry (ES-MS), together with single-crystal X-
C(CN)2]C≡CFc}(dppe)Cp and Ru{C≡CC[=C(CN)2CFc= ray studies. The M(PP)Cp' moieties give characteristic NMR
C(CN)2}(dppe)Cp.[3]
resonances for the Cp or Cp* groups and the tertiary phosphine
Scheme 1. Reaction of tcne with alkynyl-metal complexes.
ligands. Details are listed in the Experimental Section and only
specific data relating to the organic fragment will be the sub-
ject of further comment.
* Prof. Dr. M. I. Bruce
Fax: + 61-8-8303-4358
E-Mail: michael.bruce@adelaide.edu.au
[a] School of Chemistry & Physics
University of Adelaide
(i) Ru(C≡CC≡CPh)(dppe)Cp (1) and Ru(C≡CC≡CFc)(dppf)Cp (2)
Adelaide, South Australia 5005, Australia
[b] Department of Chemistry
University of Waikato
These two compounds were made by a modified route from
Me3SiC≡CC≡CR (R = Ph, Fc, respectively), RuCl(PP)Cp
(PP = dppe, dppf), KF and dbu in MeOH containing a drop of
water.[4,5] Compound 1 has been described previously,[5]
Hamilton, New Zealand
[c] Chemistry M313 SBBCS
University of Western Australia
Crawley, Western Australia 6009, Australia
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Diynyl-Ruthenium Complexes and their Adducts with Cyano-Alkenes
Scheme 2. Synthesis of Ru{C≡CC[=C(CN)2]CFc=C(CN)2}(dppf)Cp (4).
whereas 2 (Scheme 2) was characterised by a high resolution the recently described synthesis from ferrocene and tcne in
ES-MS spectrum from solutions containing NaOMe: strong sulfolane.[8]
Addition
of
FcC(CN)=C(CN)2
to
ions at m/z 954 and 977 correspond to M+ and [M + Na]+, Ru(C≡CC≡CSiMe3)(dppe)Cp*, followed by separation of the
respectively.
products by TLC, afforded two complexes identified as
Ru{C≡CC[=C(CN)2]CR=CFc(CN)}(dppe)Cp* (R 5,
=
H
SiMe3 6) (Scheme 3). The former could be obtained pure from
an analogous reaction of FcC(CN)=C(CN)2 with
Ru(C≡CC≡CH)(dppe)Cp* and likely results from ready proto-
desilylation of 6. The IR spectra contained ν(CN) bands at
2209 and 2193 (for 5) or 2213 and 2202 cm–1 (for 6) and
ν(C≡C) bands at 1987 or 1992 cm–1, respectively. The 1H
NMR spectra contained resonances at δH 6.53 (CH in 5) and
0.10 (SiMe3 in 6). Both complexes gave [M + H]+ at m/z 972
and 1044, respectively.
(ii) Ru(C≡CC≡CCPh=CBr2)(PPh3)2Cp (3)
In the reactions which afforded 4–6, there was no indication
of the formation of the isomer in which the cyano-alkene had
added to the C≡C triple bond adjacent to the metal, although
both structurally characterised isomers were obtained from the
This complex was obtained from RuCl(PPh3)2Cp and
Me3SiC≡CC≡CCPh=CBr2 following the established procedure
using KF as a desilylating reagent.[4] The dibromovinyl com-
pound was formed from Me3SiC≡CC≡CSiMe3 by a conven-
tional sequence of reactions with PhC(O)Cl/AlCl3 and CBr4/
PPh3.[6] Characterisation was routine (see Experimental Sec-
tion) and included observation of IR ν(C≡C) bands at 2136
and 2008 cm–1, Cα as a triplet at δC 102.64 [J(P,C) = 28 Hz]
and M+, [M + Na]+ and [2M + Na]+ at m/z 1000, 1023 and
2023, respectively, in the ES-MS, confirmed by high resolution
measurements.
analogous
reaction
between
tcne
and
Ru(C≡CC≡CFc)(dppe)Cp.[3] This difference may be ascribed
to the greater steric protection of the C(1)≡C(2) triple bond in
the complexes used here. For 5 and 6, the tricyanobutadienyl
compounds are formed regioselectively, with the Fc group be-
ing cis to R.
Molecular Structures
(iii) Ru{C≡CC[=(CN)2]CFc=C(CN)2}(dppf)Cp (4)
Figures 1–3 show plots of single molecules of each of the
complexes 1–3, selected bond parameters being presented in
Table 1. For the Ru(PP)Cp' centres in all complexes described
below, the geometries are pseudo-octahedral and resemble
those of many other complexes containing the same M(PP)Cp'
fragments. For these fragments, Ru–P(1,2) are 2.2515(6) to
2.311(3) Å, Ru–C(cp) are 2.22(4) to 2.282(3) Å, with angles
P(1)–Ru–P(2) between 82.80(2) and 102.54(3),the increase
from 1–3 paralleling the increase in the Ru–P distances. The
angles P(1,2)–Ru–C(1) lie between 84.90(6) and 89.4(1)°.
Addition of tcne to Ru(C≡CC≡CFc)(dppf)Cp, obtained from
RuCl(dppf)Cp and FcC≡CC≡CSiMe3 in the presence of KF
and dbu,[4] afforded orange crystals of the ring-opened adduct
Ru{C≡CC[=(CN)2]CFc=C(CN)2}(dppf)Cp 4 (Scheme 2) for
which only high resolution ES-MS data have been obtained.
Solutions containing NaOMe show no obvious M+ ion, but a
strong [M + Na]+ ion is found at m/z 1105, resulting from the
strong coordination of Na+ to the CN groups. The X-ray struc-
ture determination showed that addition had occurred to the
outer C≡C triple bond, probably as a result of steric protection
of the metal-bonded C≡C fragment by the phosphine ligand.
No evidence was found for the formation of any other product.
(i) Ru(C≡CC≡CPh)(dppe)Cp (1)
Figure 1 is a plot of a molecule of Ru(C≡CC≡CPh)(dppe)Cp
(1), from which it can be seen that the phenylbutadiynyl ligand
is attached to the metal atom through C(1) [Ru–C(1)
(iv) Ru{C≡CC[=C(CN)2]CR=CFc(CN)}(dppe)Cp* (R = H 5,
SiMe3 6).
Tricyanovinylferrocene, Fc(CN)=C(CN)2, has been de- 1.987(2) Å]. The C(1–4) chain shows the alternating short-
scribed on several occasions.[7,8] In the present study we used long-short-long C-C separations consistent with the diynyl for-
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M. I. Bruce et al.
ARTICLE
Scheme 3. Reactions of FcC(CN)=C(CN)2 with Ru(C≡CC≡CR)(dppe)Cp* (R = H, SiMe3) to give 5 and 6.
Table 1. Structure parameters for Ru(C≡CR)(PP)Cp' groups in 1–3.
Complex
1
2
3
PP
R
dppe
C≡CPh
dppf
C≡CFc
(PPh3)2
C≡CCPh=CBr2
Bond lengths /Å
Ru–P(1)
Ru–P(2)
Ru–C(cp)
(av.)
Ru–C(1)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(41)
2.2576(6)
2.2515(6)
2.2788(9)
2.2692(9)
2.2959(8)
2.2914(8)
2.239–2.250(2) 2.223–2.255(4) 2.228–2.254(3)
2.244
2.237
2.241
1.987(2)
1.227(3)
1.367(3)
1.147(7)
1.439(8)
1.999(3)
1.202(5)
1.388(5)
1.203(5)
1.438(5)
1.988(3)
1.215(5)
1.367(5)
1.222(5)
Figure 1. Plot of a molecule of Ru(C≡CC≡CPh)(dppe)Cp (1).
Bond angles /°
arations and angles at the individual carbon atoms range be-
tween 174.4(2) and 178.8(2)°, the deviations from linearity be-
ing somewhat less marked than those found for 1.
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) 172.5(2)
C(2)–C(3)–C(4) 167.4(3)
82.80(2)
84.90(6)
88.74(6)
174.5(2)
96.14(3)
89.4(1)
102.54(3)
87.59(9)
87.49(9)
178.7(3)
173.9(3)
176.7(3)
89.4(1)
174.4(3)
176.4(4)
178.8(4)
For 1: C(3)–C(4') 1.302(7), C(4')–C(41') 1.433(8) Å; C(2)–C(3)–C(4')
167.8(3), C(3)–C(4)–C(41) 172.4(6), C(3)–C(4')–C(41') 176.1(7)°. For
2: Fe(1)–C(Cp) 2.019–2.050 / 2.022–2.048(4), (av.) 2.038 / 2.036,
Fe(4)–C(Cp) 2.026–2.054(4), (av.) 2.043, P(1)–C(131) 1.830(4), P(2)–
C(231) 1.836(4) Å; C(3)–C(4)–C(401) 177.3(4)°. For 3: C(4)–C(5)
1.409(5), C(5)–C(6) 1.337(5), C(5)–C(51) 1.500(5), C(6)–Br(1,2)
1.885, 1.880(3) Å; C(3)–C(4)–C(5) 177.4(3), C(4)–C(5)–C(6)
121.2(3), C(4)–C(5)–C(51) 117.3(3), C(5)–C(6)–Br(1,2) 122.4(3),
124.1(2)°.
Figure 2. Plot of a molecule of Ru(C≡CC≡CFc)(dppf)Cp (2).
(iii) Ru(C≡CC≡CCPh=CBr2)(PPh3)2Cp (3)
mulation, the outer C≡C triple bond being considerably shorter
than that involving C(1). The usual non-linearity of the C4
chain is found [angles at individual carbons 167.4(3)–
174.5(2)°], ascribed to “crystal packing forces“ and the low
bending moment about a C(sp) carbon atom.[9]
The plot of a molecule of 3 (Figure 3) clearly shows the
alkenyl substituent on C(4) of the diynyl chain. The C–C sepa-
rations are those expected for C(sp)≡C(sp) [C(1)–C(2)
(ii) Ru(C≡CC≡CFc)(dppf)Cp (2)
The molecule of 2 (Figure 2, Table 1) differs from the dppe 1.215(5), C(3)–C(4) 1.222(5) Å] and C(sp2)=C(sp2) bonds
analogue[4a] by replacement of dppe with dppf, the parameters [C(5)–C(6) 1.337(5) Å], with a closely linear Ru–C(1–5) chain
of the Ru(dppf)Cp fragment being similar to those found ear- [angles at individual carbons are between 173.9(3) to
lier in RuH(dppf)Cp.[10] The diynyl nature of the C(1–4) chain 178.7(3)°]. Angles at the C(sp2) atoms C(5) and C(6) are be-
is confirmed by the alternating short-long-short-long C–C sep- tween 117.3(3) and 124.1(2)°.
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Diynyl-Ruthenium Complexes and their Adducts with Cyano-Alkenes
two C=C(CN)2 groups of the butadienyl cores, which have the
s-trans conformation in all three complexes. In 4, the C(3)–
C(4) bond is long [1.51(2) Å] with a C2C–C / C–CC2 inter-
planar dihedral angle of 79.8(6)°. In 5, the bonds C(3)–C(4),
C(4)–C(5) are 1.466(4), 1.340(4) Å, with the C2C–C / C–CC2
interplanar dihedral angle at C(4) being 35.1(4)°. In 6a, C(3)–
C(4) is again long [1.499(2) Å] with an associated C2C–C /
C–CCSi interplanar dihedral angle of 88.8(1)°. In 5, the C(3)–
C(4)–C(5) angle [128.5(3)°] is enlarged well above the trigonal
value. Together, these data for 5 are indicative of a substantial
contribution from the allenylidene tautomer, as suggested ear-
lier for Ru{C≡CC[=C(CN)2CFc=C(CN)2}(dppe)Cp, where the
bond length data suggest a major contribution from the allenyl-
idene
structure
Ru+{=C=C=C[C(CN)2]CFc=
Figure 3. Plot of a molecule of Ru(C≡CC≡CCPh=CBr2)(PPh3)2Cp (3). C(CN)2 }(dppe)Cp.[3] For example, the Ru–C(1) bond
[1.915(4) Å] is shorter than those found in 4–6 [1.948(2)–
–
1.96(1) Å], although the C-C distances are comparable.
(iv) Ru{C≡CC[=C(CN)2]CFc=C(CN)2}(dppf)Cp (4),
Ru{C≡CC[=C(CN)2]CR=CFc(CN)}(dppe)Cp* (R = H 5,
SiMe3 6)
Plots of molecules of 4–6 are presented in Figure 4, Fig-
ure 5, and Figure 6, with selected structural parameters col-
lected in Table 2. For 6, two polymorphs 6a (monoclinic, solv-
ated) and 6b (orthorhombic, unsolvated) were studied: the
structures are similar, but that in 6b is less precise. The cyano-
carbon ligands in these three compounds are closely similar to
those found in many complexes formed by addition of tcne to
other diynyl-ruthenium complexes.[2] The Ru–C(1) distances
in this group are somewhat shorter than those in 1–3, with the
Ru–P distances in similar ligands also being shorter. This fea-
ture probably arises from the strong electron-withdrawing
power of the cyanocarbon groups, which in turn results in a
contribution from the allenylidene tautomer. The different sub-
stituents on C(3) result in small changes in the dihedrals of the
Figure 5. Plot of
a
molecule of Ru{C≡CC[=C(CN)2]CH=
CFc(CN)}(dppe)Cp* (5).
Figure 4. Plot of
C(CN)2}(dppf)Cp (4).
a
molecule of Ru{C≡CC[=C(CN)2]CFc= Figure 6. Plot of a molecule of Ru{C≡CC[=C(CN)2]C(SiMe3)=
CFc(CN)}(dppe)Cp* (6a).
Z. Anorg. Allg. Chem. 2011, 1334–1340
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M. I. Bruce et al.
ARTICLE
[6]
Reagents: RuCl(dppf)Cp,[10] Me3SiC≡CC≡CCPh=CBr2
and
Table 2.
Structure parameters for Ru{C[=C(CN)2]CR=
[8]
CR'(CN)}(dppe)Cp' in 4–6a.
FcC(CN) = C(CN)2 were made by the cited methods.
Complex
4
5
6a
PP
Cp'
R
dppf
Cp
dppe
Cp*
H
dppe
Cp*
SiMe3
Fc
Syntheses of Complexes 1–6
Fc
(i) Ru(C≡CC≡CPh)(dppe)Cp (1): A modified procedure was em-
ployed for this synthesis.[3] A solution of RuCl(dppe)Cp (895 mg,
1.49 mmol), PhC≡CC≡CSiMe3 (300 mg, 1.51 mmol) in MeOH
(25 mL, containing 0.15 mL water) was heated to 50 °C. KF (143 mg,
2.46 mmol) and dbu (1 drop) were added and the mixture was heated
at reflux point for 45 min. After cooling to room temp., the precipitate
was collected, dried, taken up in a small amount of benzene and puri-
fied by column chromatography (basic alumina, Et2O-hexane, 1/1) to
give Ru(C≡CC≡CPh)(dppe)Cp 1 (366 mg, 36 %) as a yellow solid,
identified by comparison with the literature.[4] X-ray quality crystals
were obtained from Et2O / benzene.
R'
CN
Fc
Bond lengths /Å
Ru–P(1)
2.312(3)
2.311(3)
2.2853(8)
2.2884(8)
2.2618(5)
2.2851(5)
Ru–P(2)
Ru-C(cp)
(av.)
2.237–2.272(2) 2.230–2.282(3) 2.239–2.301(2)
2.26
2.257
2.270
Ru–C(1)
1.96(1)
1.24(2)
1.39(2)
1.51(2)
1.40(2)
1.951(3)
1.236(4)
1.391(4)
1.466(4)
1.394(4)
1.948(2)
1.231(2)
1.391(2)
1.499(2)
1.380(2)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(3)–C(30)
C(30)–C(31,32)
C(4)–C(5)
C(5)–C(51)
C(5)-C(501)
1.44, 1.43(2) 1.424, 1.427(4) 1.428, 1.432(2)
(ii) Ru(C≡CC≡CFc)(dppf)Cp (2): As for 1, solution containing
RuCl(dppf)Cp (445 mg, 0.59 mmol), FcC≡CC≡CSiMe3 (183 mg,
0.59 mmol), KF (45 mg, 0.78 mmol) and dbu (1 drop) in MeOH
(25 mL, with 0.10 mL water) was heated to reflux point for 1 h. The
mixture was cooled to room temperature, filtered and the precipitate
washed with methanol. The vacuum dried solid was subsequently puri-
fied by column chromatography (basic alumina, benzene) to afford
Ru(C≡CC≡CFc)(dppf)Cp (2) as an orange solid, which could be crys-
tallised from benzene / hexane. Anal. Calcd (C53H42Fe2P2Ru.2C6H6):
C, 70.34; H, 4.90; M, 954. Found: C, 70.08; H, 5.05 %. 1H NMR
(C6D6): δ3.68 (broad s, 2 H, C5H4 of Fc), 3.88–3.39 (m, 2 H, C5H4 of
Fc), 4.04 (broad s, 2 H, C5H4 of Fc), 4.14 (s, 5 H, C5H5 of Fc), 4.21
(broad s, 2 H, C5H4 of Fc), 4.34 (s, 5 H, C5H5Ru), 4.46–4.48 (m, 2 H,
C5H4 of Fc), 5.87 (broad s, 2 H, C5H4 of Fc), 7.00–7.13 (m, 12 H,
Ph), 7.44–7.50 (m, 4 H, Ph), 7.98–8.04 (m, 4 H, Ph). 31P NMR (C6D6):
δ56.0. ES-MS (MeOH + NaOMe, m/z): 977.049, [M + Na]+ (calcd.
977.043); 954.055, M+ (calcd. 954.052); 749, [Ru(CO)(dppf)Cp]+;
721, [Ru(dppf)Cp]+.
1.340(4)
1.436(5)
1.473(4)
1.345(2)
1.456(2)
1.470(2)
Bond angles /°
P(1)–Ru–P(2)
96.6(1)
92.3(4)
88.7(3)
167.9(1)
177.6(1)
116.8(1)
122.8(1)
84.41(3)
88.10(8)
89.24(9)
170.5(3)
167.4(3)
120.7(3)
122.5(3)
128.5(3)
121.3(3)
122.6(3)
117.2(3)
116.0(3)
80.59(2)
86.92(5)
85.60(5)
174.6(1)
173.7(2)
119.6(1)
123.1(2)
118.1(1)
119.1(1)
126.4(1)
117.8(1)
114.4(1)
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(2)–C(3)–C(30)
C(3)–C(4)–C(5)
C(4)–C(5)–C(51)
C(4)–C(5)-C(501)
C(31)–C(30)–C(32) 117.2(1)
C(51)–C(5)–C(501)
For 4: Fe(2)–C(Cp) 2.024–2.077(12), av. 2.053; Fe(3)–C(Cp) 2.042–
2.087(15), av. 2.059; C(4)–C(40) 1.39(2), C(4)–C(401) 1.46(2), C(40)–
C(41,42) 1.46, 1.45(2) Å; C(3)–C(4)–C(40) 117.4(1), C(3)–C(4)-
C(401) 116.4(1), C(41)–C(40)–C(42) 114.5(1)°. For 5: Fe–C(Cp)
2.023–2.050(3), av. 2.038 Å. For 6a: Fe–C(Cp) 2.032–2.055(2), av.
2.043; C(4)–Si(4) 1.914(2) Å; C(3)–C(4)–Si(4) 115.3(1)°.
(iii) Ru(C≡CC≡CCPh=CBr2)(PPh3)2Cp (3):
A suspension of
RuCl(PPh3)2Cp (182 mg, 0.25 mmol), Me3SiC≡CC≡CCPh=CBr2
(96 mg, 0.25 mmol), KF (15 mg, 0.25 mmol) in MeOH (10 mL, con-
taining one drop each of water and dbu) was heated at reflux point for
1 h. After cooling to room temp., the yellow precipitate was filtered
off and washed with cold MeOH. The residue was then purified on a
small basic alumina column eluting with CH2Cl2, a yellow band was
collected to give Ru(C≡CC≡CCPh=CBr2)(PPh3)2Cp (134 mg, 54 %)
as a yellow solid. Crystals suitable for the X-ray study were obtained
Conclusions
The present report describes the structures of the diynyl-ru-
thenium compounds Ru(C≡CC≡CR)(PP)Cp [R = Ph, PP =
dppe; R = Fc, PP = dppf; R = CPh=CBr2, PP = (PPh3)2], to- from CH2Cl2/hexane. Anal. Calcd (C53H40Br2P2Ru): C, 63.68; H, 4.03.
Found: C, 63.97; H, 4.27 %; M, 1000. IR (CH2Cl2): ν(C≡C) 2136,
gether with those of the polycyanobutadienyls Ru{C≡CC[=
C(CN)2]CR=CR'(CN)}(PP)Cp' [R = Fc, (PP)Cp' = (dppf)Cp;
R = H, SiMe3, (PP)Cp' = (dppe)Cp*] formed by cycloaddition
and subsequent ring-opening reactions of tcne with
Ru(C≡CC≡CFc)(dppf)Cp, or of FcC(CN)=C(CN)2 with
Ru(C≡CC≡CR)(dppe)Cp* (R = H, SiMe3). The results confirm
the direction of addition of the cyano-alkenes. They are at vari-
ance with the isolation of two isomers of the adduct between
tcne and Ru(C≡CC≡CFc)(dppe)Cp,[3] probably because of the
greater steric protection of the C(1)≡C(2) triple bond in the
present diynyl complexes.
1
2008;cm–1. H NMR (C6D6): δ = 4.36 (s, 5 H, Cp), 6.87–7.60 (m, 35
H, Ph). 13C NMR (C6D6): δ = 64.11 (s), 85.81 (s, Cp), 90.71 [t,
3J(P,C) = 2.7 Hz, Ru-C≡C), 94.48, 97.67, 127.32–133.77 (Ph), 137.99–
138.53 (Ph and Ru-C≡), 140.07. 31P NMR (C6D6): δ = 49.6. ES-MS
(MeOH + NaOMe, m/z): 1000, M+; 1023, [M + Na]+; 2023, [2M +
Na]+. High resolution MS: m/z 999.997 (calcd. 1000.001), 1022.984
(1022.990), 2022.972 (2022.993).
(iv) Ru{C≡CC[=C(CN)2]CFc=C(CN)2}(dppf)Cp (4): A mixture of
Ru(C≡CC≡CFc)(dppf)Cp (100 mg, 0.104 mmol) and tcne (16.1 mg,
0.125 mmol) was heated in refluxing thf (25mL) for 1 h. Solvent was
removed in vacuo, and the residue was purified by chromatography
(silica, CH2Cl2) to afford Ru{C≡CC[=C(CN)2]CFc=C(CN)2}(dppf)Cp
(4) as a red solid. High resolution ES-MS (MeOH + NaOMe, m/z):
Experimental Section
General experimental conditions and instrumentation were similar to 1105.059, [M + Na]+ (calcd. 1105.054). This compound was identified
those described recently.[11]
by the single-crystal X-ray structure described above.
1338 www.zaac.wiley-vch.de
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 1334–1340

Diynyl-Ruthenium Complexes and their Adducts with Cyano-Alkenes
(v) Ru{C≡CC[=C(CN)2]CR=CFc(CN)}(dppe)Cp* (R = H 5, SiMe3 7.71 (m, 20 H, Ph). 13C NMR (C6D6): δ = 10.35 (C5Me5), 30.22 [t,
6): (a)
A solution of Ru(C≡CC≡CSiMe3)(dppe)Cp* (35 mg, J(C,P) = 22 Hz, dppe], 67.63, 70.99 (C5H4), 70.83 (Cp), 77.34 (Cipso
0.043 mmol) and FcC(CN) = C(N)2 (13.3 mg, 0.043 mmol) in thf of Fc), 95.93 (C5Me5), 115.98, 117.17, 117.36 (3 × CN), other carbon
(7 mL) was stirred at room temp. for 48 h. Separation of the reaction atoms at 80.21, 119.23, 121.45, 125.29, 146.57, 127–138.00 (Ph). 31P
products by preparative TLC (silica gel, acetone-hexane 1/3) gave two NMR (C6D6): δ = 81.7 (dppe). ES-MS (MeOH / NaOMe, m/z): 1965,
major bands. The lower magenta band (Rf = 0.37) yielded Ru{C≡CC[= [2M + Na]+; 994, [M + Na]+; 972, [M + H]+.
C(CN)2]CH=CFc(CN)}(dppe)Cp* (5) (5.2 mg, 12 %), identified by
comparison with an authentic sample (below). The upper orange band
(Rf
=
0.39)
contained
Ru{C≡CC[=C(CN)2]C(SiMe3)=
Structure Determinations
CFc(CN)}(dppe)Cp* (6) (14 mg, 29 %), which formed orange crystals
(C6H6 / heptane). Anal. Calcd (C58H57FeN3P2RuSi): C, 66.80; H, 5.47;
N, 4.03; M, 1043. Found: C, 67.19; H, 5.85; N, 4.00 %. IR (cyclohex-
Full spheres of CCD area-detector diffraction data were measured us-
ing monochromatic Cu-Kα radiation, λ = 1.54184 Å (2, 3) or Mo-Kα
radiation, λ = 0.71073 Å (1, 4–6). Ntot reflections were merged to N
unique (Rint cited) after “empirical” / multiscan absorption correction
(proprietary software) and used in the full-matrix least-squares refine-
ments on F2; No with F > 4σ (F) were considered “observed”. Aniso-
tropic displacement parameter forms were refined for the non-hydro-
gen atoms, hydrogen atom treatment following a riding model.
ane): ν(CN) 2213w, 2202 (sh); ν(C≡C) 1992s cm–1. H NMR (C6D6):
1
δ = 0.10 (s, 9 H, SiMe3), 1.58 (s, 15 H, Cp*), 2.17, 3.05 (2 × m, 4 H,
dppe), 3.98, 4.52 (2 × m, 4 H, C5H4), 4.35 (s, 5 H, Cp), 6.91–7.87 (m,
20 H, Ph). 31P NMR (C6D6): δ = 79.1, 81.2 [2 × d, J(P,P) = 14 Hz,
dppe]. ES-MS (MeOH / NaOMe, m/z): 1066, [M + Na]+; 1044, [M +
H]+; 994, [M + Na + H - SiMe3]+; 971, [M + H – SiMe3]+. The reaction
also gave several unidentified decomposition products and 6 easily
underwent protodesilylation during purification.
Reflection weights were (σ2(Fo ) + (aP)2 (+ bP))–1 where P = (Fo
+
2
2
2
2Fc )/3. Neutral atom complex scattering factors were used within the
SHELXL 97 program.[12] Pertinent results are given in the figures,
which show non-hydrogen atoms with 50 % probability amplitude dis-
placement ellipsoids and hydrogen atoms with arbitrary radii of 0.1 Å)
and in Table 1, Table 2, and Table 3.
(b) A similar reaction between Ru(C≡CC≡CH)(dppe)Cp* (25 mg,
0.037 mmol) and FcC(CN) = C(CN)2 (10.5 mg, 0.037 mmol) in thf
(5 mL) afforded Ru{C≡CC[= C(CN)2]CH=CFc(CN)}(dppe)Cp* 5
(32.7 mg, 92 %) in the major magenta band, obtained as dark coloured
crystals (MeCN / Et2O). Anal. Calcd (C55H49FeN3P2Ru): C, 68.04; H, Full details of the structure determinations (except structure factors)
5.09; N, 4.33; M, 971. Found: C, 68.46; H, 5.64; N, 4.19 %. IR have been deposited with the Cambridge Crystallographic Data Centre.
(CH2Cl2): ν(CN) 2209w, 2193 (sh); ν(C≡C) 1987 s (br); other bands Copies of this information may be obtained free of charge from The
at 1744w (br), 1595w, 1465m (br), 1437m cm–1. 1H NMR (C6D6): δ = Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: +44-
1.51 (15 H, Cp*), 2.06, 3.11 (2 × m, 4 H, dppe), 4.00, 4.38 [2 × t, 1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk or www: http://
J(H,H) = 3 Hz, 2 H, C5H4], 4.12 (s, 5 H, Cp), 6.53 (s, 1 H, CH), 6.84– www.ccdc.cam.ac.uk).
Table 3. Crystal data and refinement details for complexes 1–6.
Complex
1a)
2
3
4
5
6a
6b
CCDC #
Formula
687320
804926
804932
804927
804928
804929
805355
C41H34P2Ru C53H42Fe2P2Ru C53H40Br2P2Ru C59H42Fe2N4P2Ru C55H49FeN3P2Ru C58H57FeN3P2RuSi C58H57FeN3P2RuSi
·2C6H6
1109.79
monoclinic
P21/n
13.7621(2)
19.6788(2)
18.2699(2)
·2CH2Cl2
1169.53
monoclinic
P21/n
19.0483(2)
9.8487(1)
27.1907(4)
·Me2CO
1139.75
triclinic
·2C6H6
1199.23
monoclinic
P21/n
19.2066(3)
9.3523(1)
33.2458(5)
MW
689.69
970.83
monoclinic
P21/c
11.3659(3)
25.9762(5)
16.0205(4)
1043.02
orthorhombic
Pna21
29.541(1)
9.0255(3)
19.2281(8)
Crystal system monoclinic
¯
Space group
a /Å
C2/c
P1
29.6151(5)
9.3742(3)
27.6709(9)
11.268(4)
14.502(6)
16.318(6)
99.141(6)
94.524(6)
98.279(6)
2591(2)
1.461
b /Å
c /Å
α /deg
β /deg
124.885(2)
91.556(1)
106.530(1)
108.781(3)
92.960(2)
γ /deg
V /Å3
6301.5(3)
1.454
8
0.63 [Mo-Kα] 8.0 [Cu-Kα]
0.93 0.72
4946.1(1)
1.490
4
4890.2(1)
1.589
4478.1(2)
1.440
4
5963.8(1)
1.336
4
5126.6(3)
1.351
4
0.70 [Mo-Kα]
0.81
ρc /g·cm–3
Z (f.u.)
μ /mm–1
Tmin/max
4
2
7.4 [Cu-Kα]
0.68
0.95 [Mo-Kα]
0.70
0.78 [Mo-Kα]
0.94
0.62 [Mo-Kα]
0.92
0.41 × 0.045 × 0.04 0.24 × 0.21 × 0.08
Crystal dimen- 0.40 × 0.19 × 0.09 × 0.06 × 0.13 × 0.04 × 0.26 × 0.24 ×
0.25 × 0.12 ×
0.022
sions /mm
2θmax /deg.
Ntot
0.04
65
43507
0.03
134
58439
0.03
134
42835
0.12
50
62
57381
64
55
50811
17734
8786 (0.072)
5205
85128
19995 (0.082)
9226
N (Rint
)
11204 (0.054) 8825 (0.067) 8680 (0.058)
7201
13531 (0.084)
7654
11727 (0.116)
7512
No
6289
0.035
6820
0.032
R1 [I > 2σ(I)] 0.040
0.094
0.048
0.044
0.126
wR2 (all
data)(a,b)
T /K
0.084
(0.040, –)
100(2)
0.089 (0.049, –) 0.080 (0.050, –) 0.26 (0.054, 37) 0.086 (0.030, –) 0.082 (0.029, –)
0.27 (0.078, 47)
150(2)
100(2)
150(2)
100(2)
100(2)
100(2)
a) Variata. 1. One phenyl ring of the dppe ligand and the CPh component of the alkyne were modeled as disordered over pairs of sites, occupancies
set at 0.5 after trial refinement, and with restrained geometries.
Z. Anorg. Allg. Chem. 2011, 1334–1340
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1339

M. I. Bruce et al.
ARTICLE
[5] D. J. Armitt, M. I. Bruce, B. W. Skelton, A. H. White, J. Orga-
nomet. Chem. 2008, 693, 3571.
Acknowledgement
We thank Johnson Matthey plc, Reading, UK, for a generous loan of
RuCl3.nH2O. The work was supported by the Australian Research
Council and Centre National de la Recherche Scientifique (CNRS),
France, who also funded exchanges between our laboratories through
IREX, Linkage Exchange and travel grants.
[6] T. Luu, E. Elliott, A. D. Slepkov, S. Eisler, R. MacDonald, F. A.
Hegmann, R. R. Tykwinski, Org. Lett. 2005, 7, 51.
[7] a) V. N. Nemykin, N. Kobayashi, Chem. Commun. 2001, 165;
b) V. A. Nefedov, B. P. Bospalov, V. V. Titov, Zhur. Org. Khim.
1974, 10, 1553; c) E. G. Perevalova, D. A. Lemenovskii, V. P.
Alekseev, K. I. Grandberg, A. N. Nesmeyanov, Izv. Akad. Nauk
SSSR Ser. Khim. 1972, 1867.
[8] a) V. N. Nemykin, A. Y. Maximov, A. Y. Koposov, Organome-
tallics 2007, 26, 3138; b) V. N. Nemykin, E. A. Makarova, J. O.
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[9] S. Szafert, J. A. Gladysz, Chem. Rev. 2003, 103, 4175; S. Szafert,
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Received: March 15, 2011
Published Online: May 23, 2011
1340
www.zaac.wiley-vch.de
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 1334–1340