The pentynoate ligand as a building block for multimetallic systems

Article abstract of DOI:10.1002/ejic.201301504

The complexes [RuRCl(CO)(BTD)(PPh₃)₂] (R = CH=CHtBu, CH=CHC₆H₄Me-4, CH=CHC₅H₄FeC ₅H₅; BTD = 2,1,3-benzothiadiazole) and [Ru{C(C≡CPh)=CHPh}(CO)(PPh₃)₂] reacted with pentynoic acid to yield the same complex, [RuCl(O₂CCH ₂CH₂C≡CH)(CO)(PPh₃)₂], through cleavage of the vinyl ligand. In contrast, the products [RuR(O ₂CCH₂CH₂C≡CH)(CO)(PPh₃) ₂] were formed when NaO₂CCH₂CH ₂C≡CH was used. An osmium example, [Os(CH=CHC₆H ₄Me-4)(O₂CCH₂CH₂C≡CH)(CO) (PPh₃)₂], was also prepared from treatment of [Os(CH=CHC₆H₄Me-4)Cl(CO)(BTD)(PPh₃) ₂] with NaO₂CCH₂CH₂C≡CH. Coupling of the pendant alkyne in [RuCl(O₂CCH₂CH ₂C≡CH)(CO)(PPh₃)₂] to yield the homodimetallic complex [{RuCl(O₂CCH₂CH₂C≡ C)(CO)(PPh₃)₂}₂] was achieved by using [PdCl₂(PPh₃)₂], CuI and NEt₃. The reactivity of the alkyne unit was further exploited by the metallation of the alkyne with ClAu(PR₃) (R = Ph, Cy) and Co₂(CO)₈ to yield the multimetallic species [Ru(CH=CHC₆H₄Me-4) (O₂CCH₂CH₂C≡CAuPR₃)(CO) (PPh₃)₂] and [Ru(CH=CHC₆H₄Me-4) (O₂CCH₂CH₂CC{Co₂(CO) ₆}H)(CO)(PPh₃)₂]. The structures of the complexes [Ru(CH=CHC₆H₄Me-4)(O₂CCH ₂CH₂C≡CH)(CO)(PPh₃)₂] and [Ru(CH=CHtBu)(O₂CCH₂CH₂C≡CH)(CO)(PPh ₃)₂] were determined crystallographically. Organometallic ruthenium and osmium pentynoate complexes were prepared, and the pendant alkyne functionality was used to form homodimetallic and heteronuclear di- and trimetallic complexes. Copyright

Full text of DOI:10.1002/ejic.201301504

FULL PAPER
DOI:10.1002/ejic.201301504
The Pentynoate Ligand as a Building Block for
Multimetallic Systems
Yvonne H. Lin,[a] Loraine Duclaux,[b] Ferran Gonzàlez de Rivera,[b]
Amber L. Thompson,[a] and James D. E. T. Wilton-Ely*[b]
Keywords: Ruthenium / Osmium / Heterometallic complexes / Alkynes / Carboxylate ligands
The complexes [RuRCl(CO)(BTD)(PPh3)2] (R = CH=CHtBu,
CH=CHC6H4Me-4, CH=CHC5H4FeC5H5; BTD 2,1,3-
(PPh3)2] to yield the homodimetallic complex [{RuCl-
(O2CCH2CH2CϵC)(CO)(PPh3)2}2] was achieved by using
[PdCl2(PPh3)2], CuI and NEt3. The reactivity of the alkyne
unit was further exploited by the metallation of the alkyne
with ClAu(PR3) (R = Ph, Cy) and Co2(CO)8 to yield the multi-
metallic species [Ru(CH=CHC6H4Me-4)(O2CCH2CH2Cϵ
CAuPR3)(CO)(PPh3)2] and [Ru(CH=CHC6H4Me-4)(O2CCH2-
CH2CC{Co2(CO)6}H)(CO)(PPh3)2]. The structures of the com-
=
benzothiadiazole) and [Ru{C(CϵCPh)=CHPh}(CO)(PPh3)2]
reacted with pentynoic acid to yield the same complex,
[RuCl(O2CCH2CH2CϵCH)(CO)(PPh3)2], through cleavage of
the vinyl ligand. In contrast, the products [RuR-
(O2CCH2CH2CϵCH)(CO)(PPh3)2] were formed when NaO2-
CCH2CH2CϵCH was used. An osmium example,
[Os(CH=CHC6H4Me-4)(O2CCH2CH2CϵCH)(CO)(PPh3)2],
was also prepared from treatment of [Os(CH=CHC6H4Me-4)-
Cl(CO)(BTD)(PPh3)2] with NaO2CCH2CH2CϵCH. Coupling
of the pendant alkyne in [RuCl(O2CCH2CH2CϵCH)(CO)-
plexes
[Ru(CH=CHC6H4Me-4)(O2CCH2CH2CϵCH)(CO)-
(PPh3)2] and [Ru(CH=CHtBu)(O2CCH2CH2CϵCH)(CO)-
(PPh3)2] were determined crystallographically.
rical.[3,4] The vinyl ligand itself can be utilised to bridge the
metal centres[4] or bifunctional linkages such as diamines,[5]
diisocyanides,[5] dithiocarbamates[1c] or xanthates can be
employed.[2a] We have reported a diruthenium compound
prepared from a ferrocene dicarboxylate bridge; however,
this constitutes only one of a few examples in which dicarb-
oxylates have been used to link vinyl units.[6] Even straight-
forward routes to dinuclear compounds of this type can be
problematic. Although di- and tricarboxylates are used to
great effect to form metal–organic frameworks (MOFs),[7]
they usually offer only a symmetrical arrangement of metal
ions about the linkage. Drawbacks can also unexpectedly
occur, as demonstrated by the resolutely insoluble products
obtained from attempts to link vinyl complexes by using
sodium terephthalate [C6H4(CO2Na)-1,4].[6]
Although routes to symmetrical homodimetallic com-
plexes are abundant, few approaches exist for the prepara-
tion of heterodimetallic organometallic complexes. In this
report, we describe the use of group 8 complexes and how
the pentynoate ligand can be used to coordinate a first
metal centre through the oxygen donors and leave the pen-
dant alkyne moiety available for the subsequent coordina-
tion of a different metal unit.
Introduction
The field of multimetallic compounds is a fascinating
area of research at the interface between coordination and
materials chemistry. The structural and electrochemical
properties of such materials allow them to be used for a
diversity of applications, such as sensing or catalysis.
The linking of organotransition metal complexes can be
achieved either through the organic moiety or through a
polyfunctional spacer ligand. Given that the construction
of symmetrical homodimetallic ensembles is often relatively
straightforward, one of the challenges in this area is the
development of methodologies that allow the controlled
preparation of heteromultimetallic species. This is an area
in which we have successfully employed bifunctional dithio-
carbamate ligands[1] and, more recently, spacers with both
carboxylate and xanthate functionalities.[2] The key aspect
of such approaches is the accessibility of heterodimetallic
systems. Relatively few dimetallic complexes with vinyl or
other organic ligands are known and almost all are symmet-
[a] Chemistry Research Laboratory, University of Oxford,
Mansfield Road, Oxford OX1 3TA, United Kingdom
[b] Department of Chemistry, Imperial College London, South
Kensington Campus,
Such multimetallic compounds have potential in many
fields in which the incorporation of different metal centres
into the same molecular framework is desired so that the
properties of different metal centres (catalysis, electrochem-
istry, cytotoxicity, luminescence, etc.) are available for ex-
London SW7 2AZ, UK
E-mail: j.wilton-ely@imperial.ac.uk
www.imperial.ac.uk/people/j.wilton-ely
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201301499.
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ploitation within the same system. We believe that commer- obtained
from
the
reaction
of
[Ru(R)Cl-
cially available pentynoic acid could serve as a useful ligand (CO)(BTD)(PPh3)2] (R = CH=CHtBu, CH=CHC5H4-
in this respect.
FeC5H5) or [Ru(C(CϵCPh)=CHPh)(CO)(PPh3)2] with
pentynoic acid.
Results and Discussion
The compounds [RuHCl(CO)L2/3] (L = PiPr3,[8] PPh3)[9]
provide a convenient and versatile entry point for the study
of group 8 vinyl complexes[10] and they have played a cen-
tral role in fundamental work in the area.[11–16] The most
convenient triphenylphosphine-stabilised vinyl complexes to
use as starting materials are those of the form
[Ru(CR1=CHR2)Cl(CO)(PPh3)2][9] or [Ru(CR1=CHR2)Cl-
(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole),[15c] in
which BTD is a labile ligand. A marked advantage of the
latter is that it avoids contamination with tris(phosphine)
material. As might be expected for such a ubiquitous li-
gand, many examples of organometallic carboxylate com-
plexes of the heavier congeners of group 8 are known.[10]
Carboxylate compounds that also contain a vinyl ligand are
known for ruthenium[8,11b,17,18] and osmium.[8,12f,12g,18]
However, no examples of these metals with the pentynoate
ligand have been reported.
Scheme 1. Formation of ruthenium pentynoate species. R1 = H, R2
= C6H4Me-4 (2), R2 = tBu (3), R2 = Fc (5); R1 = CϵCPh, R2 =
Ph (4); L = 2,1,3-benzothiadiazole (BTD) or no ligand.
In 1998, Ros and co-workers reported that the addition
The treatment of 1 with an ethanolic solution of sodium
of pentynoic acid to [RuHCl(CO)(PPh3)3] leads to the borohydride did not lead cleanly to the corresponding hy-
pentenoate complex [RuCl(O2CCH2CH2CH=CH2)(CO)- dride [RuH(O2CCH2CH2CϵCH)(CO)(PPh3)2]. Instead,
(PPh3)3], though the mechanism of hydrogen transfer to the modest amounts of the pentenoate compound [Ru-
triple bond is not completely clear.[19] Thus, we decided to Cl(O2CCH2CH2CH=CH2)(CO)(PPh3)2] were isolated,
investigate the reactivity of pentynoic acid with the vinyl though the mechanism for this is unclear.
complexes [Ru(CR1=CHR2)Cl(CO)(BTD)(PPh3)2], which
have no hydride functionality.
Although cleavage of the vinyl ligand is observed on the
addition of pentynoic acid, if the acid is deprotonated first,
The addition of pentynoic acid to a dichloromethane the vinyl ligand can be retained in the product. Thus, the
solution of [Ru(CH=CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] complex [Ru(CH=CHC6H4Me-4)(O2CCH2CH2CϵCH)-
yielded a yellow complex after workup. A mutually trans (CO)(PPh3)2] (2) was successfully obtained on reaction of
disposition of the phosphine ligands in the product was [Ru(CH=CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] with pent-
indicated by a singlet in the 31P NMR spectrum at δ = ynoic acid prestirred with NaOMe (Scheme 1). In contrast
35.7 ppm. However, no resonances due to vinyl protons to the reaction without base, the vinyl protons were clearly
1
were observed in the region δ = 4–6 ppm. Two multiplets evident in the H NMR spectrum with a doublet of triplets
attributed to the ethylene protons of the organic ligand were at δ = 7.73 ppm for the α-H proton and a doublet at δ =
1
seen at δ = 1.06 and 1.26 ppm in the H NMR spectrum 5.91 ppm for β-H with a mutual coupling of 15.7 Hz. The
along with a triplet at δ = 1.68 ppm with a small coupling tolyl substituent gave rise to typical resonances, and the
(JH,H = 2.6 Hz). Absorptions in the solid-state infrared same features were observed for the pentynoate ligand as
spectrum (Nujol/KBr) were observed for νCO and νC–O at those for 1 with multiplets at δ = 1.11 and 1.39 ppm and
1941 and 1515 cm–1 along with a νCϵC band at 2121 cm–1. an acetylenic proton resonance at δ = 2.09 ppm (JH,H
=
These data indicated that, rather than hydrogenation 2.7 Hz). Single crystals of 2 were grown, and one was used
of the alkyne, the carboxylate complex [Ru- for a structural study, as shown in Figure 1. Further dis-
Cl(O2CCH2CH2CϵCH)(CO)(PPh3)2] (1) had formed cussion of the structure can be found in the Structural Sec-
(Scheme 1). A molecular ion at m/z = 786 and satisfactory tion. The treatment of 2 with HCl on an NMR scale cleaved
elemental analysis confirmed the overall composition of the the vinyl group and generated 1 (1H and 31P NMR spec-
compound. The cleaved vinyl ligand was isolated after troscopy).
workup of the ethanol filtrate in the form of the alkene E-
Two further examples were prepared from [Ru(CH=CH-
H2C=C(H)C6H4Me-4 [1H NMR spectroscopy: δ = 5.26 tBu)(CO)Cl(BTD)(PPh3)2] and [Ru{C(CϵCPh)=CHPh}Cl-
(JH,H = 10.9 Hz), 5.78 (JH,H = 17.6 Hz), 6.77 (JH,H = 17.6, (CO)(PPh3)2] in the same manner. These reactions yielded
10.9 Hz) ppm]. This is consistent with the observation that pentynoate products bearing an alkyl-substituted vinyl and
[RuHCl(CO)(PPh3)3] reacts with FcCO2H (Fc = ferrocenyl) an enynyl ligand, namely, [RuR(O2CCH2CH2CϵCH)-
to give [RuCl(O2CFc)(CO)(PPh3)2],[17g] although two iso- (CO)(PPh3)2] [R = CH=CHtBu (3); C(CϵCPh)=CHPh]
mers resulted from that reaction. Compound 1 was also (4). The ferrocenyl variant [Ru(CH=CHFc)Cl(CO)(BTD)-
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Figure 1. Molecular structure of the cation in 2. Selected bond
lengths [Å] and angles [°]: Ru1–C49 1.813(3), Ru1–P1 2.3663(7),
Ru1–P21 2.3662(7), C55–C57 1.208(18), P2–Ru1–P21 177.03(4).
Further bond data are given in Table 1.
Figure 2. Molecular structure of the cation in 3. Selected bond
lengths [Å] and angles [°]: Ru1–C47 1.817(3), Ru1–P2 2.3595(7),
Ru1–P21 2.3652(7), C450–C460 1.180(2), P2–Ru1–P21 175.64(3).
Further bond data are given in Table 1.
(PPh3)2] was used to synthesise a dimetallic complex
[Ru(CH=CHFc)(O2CCH2CH2CϵCH)(CO)(PPh3)2] (5, Fc
= C5H4FeC5H5). Compound 3 was also the subject of a [{RuCl(O2CCH2CH2CϵC)(CO)(PPh3)2}2] (7) in 76% yield
crystallographic study (Figure 2). For further discussion, (Scheme 2). Although the spectroscopic data for the com-
see Structural Section.
pound were similar to those for 1, the absence of an acetyl-
1
By using the same approach, an osmium example was enic proton resonance in the H NMR spectrum indicated
generated from [Os(CH=CHC6H4Me-4)Cl(CO)(BTD)- that a new product had been formed. This was further sup-
(PPh3)2] to yield [Os(CH=CHC6H4Me-4)(O2CCH2CH2- ported by diagnostic fragmentations in the FAB mass spec-
CϵCH)(CO)(PPh3)2] (6). Similar spectroscopic features trum at m/z = 1478 for the loss of a chloride ligand and
were found to those observed for 2. The only noteworthy two carbon monoxide ligands. The formulation was also
difference was the slightly lower frequency νCO absorption supported by the good agreement of the elemental analysis
(1901 cm–1) owing to the more electron-rich osmium centre. with the calculated values. The Signer osmometry
This complex is one of only a few osmium carboxylate com- method,[21] which is based on the fact that the vapour pres-
plexes that also bear vinyl functionality.[8,12f,12g,18]
sure of a solution depends upon the mole fraction of dis-
With a range of pentynoate complexes prepared, the re- solved solute, was also employed to confirm that the prod-
activity of the pendant alkyne was then explored. The cou- uct was indeed approximately twice the mass of the precur-
pling of alkynes to give diynes can be achieved by using a sor 1 (see Supporting Information for details). This method
number of catalysts.[20] One of the best-known systems is gave the molecular mass to be 1503 Daltons, which is within
[PdCl2(PPh3)2] with CuI and NEt3, and this was used to the expected 5% error of the calculated value for 7 of 1570
convert 1 to the symmetrical homodimetallic complex Daltons.
Scheme 2. Routes to di- and trimetallic species. L = PPh3.
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Gold acetylide complexes are well established in the lit- try[24a] concept. There are relatively few successful examples
erature[22] and are readily formed from the treatment of an of this reaction with metal-containing substrates.[24b] The
alkyne with a base and [AuCl(L)] (L = PR3, CNR, etc.). most relevant is that reported by Ren and co-workers with
The successful formation of [Ru(CH=CHC6H4Me- “paddlewheel” diruthenium complexes.[24c]
4)(O2CCH2CH2CϵCAuPPh3)(CO)(PPh3)2] (8) from 2 and
However, repeated attempts to couple the pendant alkyne
[AuCl(PPh3)] in the presence of 1,8-diazabicycloundec-7- of 1 or 2 with benzylazide failed to yield any reaction.
ene (DBU; Scheme 2) was indicated initially by the appear- Many different protocols were employed, ranging from the
ance of a new singlet at δ = 42.2 ppm in the 31P NMR copper(II) sulfate/ascorbate and copper(II) acetate systems
spectrum. This feature was distinct from the typically to ones employing copper(I) salts, [Cu(NCMe)4]BF4, [CuI-
higher-field resonance of the ruthenium-bonded PPh3 li- (IAd)] and [CuBr(PPh3)3]. The reasons for this are unclear
gands (at δ = 37.7 ppm and with twice the intensity). The other than there may be unfavourable interactions with the
lack of spectroscopic features in the 1H NMR spectrum for (coordinatively-saturated) ruthenium centre or the oxygen
the new moiety led to the spectrum appearing unchanged donors of the carboxylate ligand. No decomposition was
other than greater activity in the aromatic region, which observed, and the successful reaction of more bulky units
integrated to 45 protons. However, the new metal acetylide such as dicobalt octacarbonyl would suggest that straight-
unit was observed in the solution infrared spectrum forward steric factors are not to blame.
(CH2Cl2) with a νCϵC band at 2058 cm–1 (shifted from
To probe the steric constraints of the system, the reaction
2145 cm–1 in the precursor 2) and νCϵO and νC=O absorp- of 1, 2 and 3 with one equivalent of [MHCl(CO)-
tions at 1917 and 1523 cm–1. A molecular ion at m/z = 1326 (BTD)(PPh3)2] (M = Ru, Os) was attempted in dichloro-
and good agreement of the elemental analysis confirmed methane to achieve the insertion of the pendant alkyne into
the overall composition. The complex [Ru(CH=CH- the M–H bond to form the dinuclear vinyl compounds
C6H4Me-4)(O2CCH2CH2CϵCAuPCy3)(CO)(PPh3)2]
(9) [(PPh3)2(OC)(R)Ru{O2CCH2CH2CH=(H)C}M(CO)Cl-
was also prepared from 2 and [AuCl(PCy3)] in the presence (BTD)(PPh3)2] (R = Cl, CH=CHC6H4Me-4, CH=CHtBu;
of DBU. Similar spectroscopic features as those for 8 were M = Ru, Os); however, the reaction was sluggish and led to
observed, apart from those associated with the tricyclohex- multiple products. Increasing the reaction duration (from
ylphosphine ligand (singlet at δ = 56.4 ppm in the 31P NMR hours to days) or elevating the temperature (reflux in
spectrum, and resonances between δ = 1.42 and 2.04 ppm CHCl3 or 1,2-dichloroethane) did not improve the outcome.
1
in the H NMR spectrum). When the gold complex [Au- It is likely that the observed reactivity is due to the steric
Cl(IDip)] [IDip = 1,3-bis(2,6-diisopropylphenyl)imidazol-2- congestion caused by the close proximity of four PPh3 units.
ylidene] was employed in the same manner, a mixture of
Unfortunately, despite repeated attempts with a wide
products was obtained including triphenylphosphine and its range of solvent combinations (both vapour diffusion and
oxide, apparently because of the displacement of a phos- layering techniques) further structural characterisation of
phine ligand by the N-heterocyclic carbene ligand.
the polymetallic species was hampered by a lack of suitable
A trimetallic example was obtained from the well-estab- crystal morphology (size, twinning, desolvation even at
lished reaction of an alkyne with dicobalt octacarbonyl 90 K). In addition, it is possible that the difficulty in regular
(Scheme 2). The treatment of [Ru(CH=CHtBu)(O2- packing of unsymmetrical compounds (such as 8, 9 and 10)
CCH2CH2CϵCH)(CO)(PPh3)2] (3) with Co2(CO)8 resulted is a barrier to crystallisation as we have found in earlier
in the evolution of carbon monoxide and the formation of studies of symmetrical multimetallic compounds.
[Ru(CH=CHtBu)(O2CCH2CH2CC{Co2(CO)6}H)(CO)-
(PPh3)2] (10). The disappearance of the νCϵC absorption
indicated that the pendant alkyne had reacted. However,
Structural Section
the retention of the pentynoate ligand was indicated by
1
multiplets at δ = 1.09 and 2.00 ppm in the H NMR spec-
In all complexes, the geometry at the metal centre is a
trum, and a resonance for the acetylenic proton was ob- slightly distorted octahedral arrangement. As shown in
served at much lower field (δ = 5.71 ppm) than the corre- Table 1, the bite angle of the carboxylate ligand does not
sponding feature in the starting material. This chemical vary between 2 and 3, and the value is similar to those re-
shift value agrees well with those reported in the literature ported for the surprisingly small number of ruthenium
for organic (hexacarbonyldicobalt)alkynes.[23] The vinyl li- carboxylate complexes that also bear a vinyl ligand. The
gand gave rise to a singlet at δ = 0.72 ppm (Me) and two most relevant example is [Ru(CH=CHPh)(O2CMe)(CO)-
doublets at 5.13 (β-H) and 6.62 (α-H) ppm with a mutual (PPh3)2],[17e] which displays a smaller O–Ru–O angle of
coupling of 15.3 Hz. In the solid-state IR spectrum, the νCO 55.9(4) Å. The carboxylate ligand bonds to the metal in an
absorption at 1941 cm–1 was assigned to the carbonyl ligand asymmetrical fashion owing to the trans influence of the
attached to the ruthenium centre, whereas the “Co2(CO)6” other equatorial ligands. In 2 and 3, the differences are con-
unit gave rise to absorptions in the region 2024–2089 cm–1. siderable, and the superior trans influence of the vinyl li-
The presence of a pendant terminal alkyne, which dis- gand over the carbonyl ligand is indicated by the elongated
plays reactivity analogous to that of free alkynes, led us to Ru–O bond trans to the vinyl ligand. The Ru–Cα bond
explore the copper-catalysed cycloaddition of azides as this lengths of the vinyl ligand are comparable to those reported
is now established as a central part of the “click” chemis- for previous examples (Table 1), and the Ru–Cα–Cβ angle
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Table 1. Bond lengths [Å] and angles [°] for 2 and 3 and other vinyl complexes bearing carboxylate ligands; L = PPh3.
Complex
Ru–Cα
Ru–Cα–Cβ
Ru–O
O–Ru–O
Ref.
[17g]
[17e]
[6]
[Ru(CH=CH2)(O2CFc)(CO)L2]
2.073(7)
2.030(15)
2.069(5)
122.4(7)
125.6(8)
129.6(4)
121.5(2)
123.4(2)
2.192(3), 2.269(3)
2.381(11), 2.259(10)
2.250(4), 2.237(3)
2.174(2), 2.288(3)
2.204(4), 2.276(4)
58.65(13)
55.9(4)
58.16(13)
58.53(9)
58.47(10)
[Ru(CH=CHPh)(O2CMe)(CO)L2]
[Ru{C(CϵCPh)=CHPh}(O2CFc)(CS)L2]
[2]
[Ru(CH=CHC6H4Me-4)(O2CCH2CH2CϵCH)(CO)L2] 2.043(3)
[3]
[Ru(CH=CHtBu)(O2CCH2CH2CϵCH)(CO)L2]
2.051(3)
Os),[15h]
[Ru(CH=CHC5H4FeC5H5)Cl(BTD)(CO)(PPh3)2],[1c]
of the vinyl ligand is much more susceptible to the steric
environment and varies from 121.5(2) Å in 2 to 129.6(4) Å
for the bulky enynyl ligand in [Ru{C(CϵCPh)=CHPh}-
(O2CFc)(CS)(PPh3)2].[6] There is significant disorder of the
pendant alkyne moiety, which lies in two positions in both
2 and 3. The bond length of the pendant alkyne is around
1.19 Å in 2 and 3; however, the disorder in this part of the
ligand makes such comparisons unreliable.
[AuCl(PPh3)][31] and [AuCl(PCy3)].[32] MALDI-MS and FAB-MS
data were obtained by using Micromass TofSpec and Autospec Q
instruments, respectively. Infrared data were obtained by using a
Perkin–Elmer Paragon 1000 FTIR (Nujol mull on KBr plates) or
a Perkin–Elmer Spectrum 100 FTIR spectrometer. Characteristic
phosphine-associated infrared data were present in all compounds
but are not reported. NMR spectroscopy was performed at 25 °C
by using a Varian Mercury 300 spectrometer with samples in
CDCl3 unless otherwise indicated. All couplings are in Hertz, and
31P NMR spectra are proton-decoupled. Elemental analysis data
were obtained at the London Metropolitan University. The pro-
cedures given provide materials of sufficient purity for synthetic
and spectroscopic purposes. Samples for elemental analysis were
recrystallised from a mixture of dichloromethane and ethanol. Sol-
Conclusions
This report describes a new way to link metal centres in
an unsymmetrical manner by using commercially available
pentynoic acid, and σ-vinyl compounds of group 8 metals
were used as model complexes. The carboxylate function-
ality is particularly versatile and coordinates readily to most
transition metals, and the pendant alkyne can be utilised to
add a second metal at a later stage. This has been illustrated
in the preparation of dimetallic (RuRu, RuAu) and trime-
tallic (RuCoCo) examples. The well understood yet dif-
fering reactivity of transition metal fragments towards carb-
oxylate and alkyne units should allow multimetallic com-
pounds to be constructed in a controlled, stepwise fashion
by this approach.
Potential applications of the multimetallic compounds
discussed above could exploit the well-established electro-
chemistry of ruthenium(II) and osmium(II) compounds[25]
in combination of a property introduced by the second
metal centre. Functionalities such as the Co2(CO)6 unit
could be employed in the rapidly growing field of carbon
monoxide releasing molecules (CO–RMs),[26] and the ad-
dition of metal acetylide units by using the pendant alkyne
could offer potential in the area of nonlinear optic (NLO)
materials, in which gold(I) acetylides are prominent.[27] Ad-
ditionally, the luminescence properties of gold(I) acetylides
have been noted,[28] and this feature could also be incorpo-
rated into systems through the use of a simple, inexpensive
linker such as pentynoic acid.
1
vates were confirmed by integration of the H NMR spectra.
[RuCl(O2CCH2CH2CϵCH)(CO)(PPh3)2] (1): Pentynoic acid
(34 mg, 0.347 mmol) was added to a dichloromethane solution
(20 mL)
(300 mg, 0.318 mmol). The mixture was stirred at room tempera-
ture for 1 h, and ethanol (30 mL) was added; slow concentration
under reduced pressure provided a yellow product. The product
was collected by filtration, washed with ethanol (20 mL) and hex-
ane (10 mL) and dried under vacuum. The product was recrystal-
lised from dichloromethane and ethanol, yield 211 mg (84%). IR:
of
[Ru(CH=CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2]
ν = 2121 (νCϵC), 1941 (νCO), 1515 (νOCO), 1458, 1336, 1313, 1243,
˜
1187, 880, 642 cm–1. 1H NMR: δ = 1.06, 1.26 (mϫ2, 2ϫ2 H,
CH2), 1.68 (t, JH,H = 2.6 Hz, 1 H, CCH), 7.39–7.57 (m, 30 H,
C6H5) ppm. 31P NMR: δ = 35.7 (s, PPh3) ppm. MS (FAB): m/z (%)
= 786 (20) [M]+. C42H35ClO3P2Ru·0.75CH2Cl2 (849.90): calcd. C
60.4, H 4.3; found C 60.3, H 4.2.
[Ru(CH=CHC6H4Me-4)(O2CCH2CH2CϵCH)(CO)(PPh3)2] (2):
Pentynoic acid (68.7 mg, 0.700 mmol) was stirred with NaOMe
(113 mg, 2.092 mmol) in a mixture of dichloromethane (60 mL)
and methanol (60 mL) for 30 min. Solid [Ru(CH=CHC6H4Me-4)
Cl(CO)(BTD)(PPh3)2] (600 mg, 0.637 mmol) was added to the
solution, and the reaction mixture was stirred at room temperature
for 2 h. Slow concentration under reduced pressure provided a yel-
low product, which was collected by filtration, washed with ethanol
(20 mL) and hexane (10 mL) and dried under vacuum, yield
518 mg (94%). IR (KBr/Nujol): ν = 2145 (νCϵC), 1923 (νCO), 1528
˜
(νOCO) cm–1. H NMR ([D6]acetone): δ = 1.11, 1.39 (mϫ2, 2ϫ2
1
H, CH2), 2.09 (t, JH,H = 2.7 Hz, 1 H, CCH), 2.13 (s, 3 H, CH3),
5.91 (d, JH,H = 15.7 Hz, 1 H, β-H), 6.35, 6.74 (AB, JA,B = 8.1 Hz,
4 H, C6H4), 7.45–7.50 (m, 30 H, C6H5), 7.73 (dt, JH,H = 15.7, JH,P
= 2.8 Hz, 1 H, α-H) ppm. 31P NMR: δ = 37.8 (s, PPh3) ppm. MS
(FAB): m/z (%) = 868 (24) [M]+. C51H44O3P2Ru (867.92): calcd. C
70.6, H 5.1; found C 70.8, H 5.0.
Experimental Section
General Comments: All experiments were performed under aerobic
conditions, and the majority of the complexes appear indefinitely
stable towards the atmosphere in solution and in the solid state.
Solvents were used as received from commercial sources. The fol-
[Ru(CH=CHtBu)(O2CCH2CH2CϵCH)(CO)(PPh3)2] (3): The
same procedure was followed as that for 2 with pentynoic acid
(35.6 mg, 0.363 mmol), NaOMe (58.9 mg, 1.090 mmol) and
lowing
complexes
have
been
described
elsewhere:
[RuHCl(CO)(PPh3)3],[29]
[Ru{C(CϵCPh)=CHPh}Cl(CO)-
(PPh3)2],[15a,15b]
[Ru(CH=CHtBu)Cl(CO)(BTD)(PPh3)2],[30] [Ru(CH=CHtBu)Cl(CO)(BTD)(PPh3)2] (300 mg, 0.330 mmol) in
[M(CH=CHC6H4Me-4)Cl(BTD)(CO)(PPh3)2] (M
=
Ru,[15c] methanol (30 mL) and dichloromethane (30 mL) to yield a yellow
Eur. J. Inorg. Chem. 2014, 2065–2072
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product (247 mg, 90%). IR (KBr/Nujol): ν = 2121 (νCϵC), 1908 (FAB): m/z (%) = 1478 (1) [M – Cl – 2CO]+. C84H68Cl2O6P4Ru2
˜
(νCO), 1533 (νOCO) cm–1. 1H NMR (CD2Cl2): δ = 0.01 (s, 9 H, Bu), (1570.40): calcd. C 64.2, H 4.4; found C 64.3, H 4.4.
0.67, 1.01 (mϫ2, 2ϫ2 H, CH2), 1.34 (br s, 1 H, CCH), 4.62 (dt,
[Ru(CH=CHC6H4Me-4){O2CCH2CH2(CϵCAuPPh3)}(CO)-
JH,H = 15.0 Hz, JH,P = 1.8 Hz, 1 H, β-H), 5.94 (dt, JH,H = 15.0 Hz,
(PPh3)2] (8): To 2 (50 mg, 0.058 mmol) in dichloromethane
JH,P = 2.0 Hz, 1 H, α-H), 7.02–7.07 (m, 30 H, C6H5) ppm. 31P
(20 mL), a few drops of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)
NMR: δ = 38.1 (s, PPh3) ppm. MS (FAB): m/z (%) = 834 (10)
were added. [AuCl(PPh3)] (28.5 mg, 0.058 mmol) was then added,
[M]+. C48H46O3P2Ru (833.90): calcd. C 69.1, H 5.5; found C 69.0,
and the mixture was stirred in the dark overnight. Ethanol (20 mL)
H 5.6.
was added, and a yellow solid was obtained by slow concentration
under reduced pressure with a rotary evaporator. The product was
collected by filtration, washed with cold ethanol (10 mL) and hex-
ane (10 mL) and dried under vacuum. The product was slightly
[Ru{C(CϵCPh)=CHPh}(O2CCH2CH2CϵCH)(CO)(PPh3)2] (4):
The same procedure was followed as that for 2 with pentynoic acid
(72.6 mg, 0.740 mmol), NaOMe (119 mg, 2.203 mmol) and
[Ru{C(CϵCPh)=CHPh}Cl(CO)(PPh3)2] (600 mg, 0.673 mmol) in
soluble in ethanol, which resulted in a low yield, yield 33 mg (43%).
IR (KBr/Nujol): ν = 2058 (νCϵC), 1917 (νCO), 1523 (νOCO) cm–1.
˜
methanol (60 mL) and dichloromethane (60 mL) to yield a yellow
1H NMR (CD2Cl2): δ = 1.17, 1.50 (mϫ2, 2ϫ2 H, CH2), 2.18 (s,
3 H, CH3), 5.79 (d, JH,H = 15.6 Hz, 1 H, β-H), 6.34, 6.78 (AB, JA,B
product (532 mg, 83%). IR (KBr/Nujol): ν = 2150, 2122 (νCϵC),
˜
1919 (νCO), 1526 (νOCO) cm–1. 1H NMR: δ = 1.09, 1.38 (mϫ2,
= 8.0 Hz, 4 H, C6H4), 7.36–7.53 (m, 45 H, C6H5), 7.73 (dt, JH,H
=
2ϫ2 H, CH2), 1.68 (t, JH,H = 2.7 Hz, 1 H, CCH), 6.93 (t, JH,H
=
15.6 Hz, JH,P = 2.7 Hz, 1 H, α-H) ppm. 31P NMR: δ = 37.7 (s,
RuPPh3), 42.2 (s, AuPPh3) ppm. MS (FAB): m/z (%) = 1326 (5)
[M]+. C69H58AuO3P3Ru (1326.15): calcd. C 62.5, H 4.4; found C
62.6, H 4.3.
7.90 Hz, 2 H, 1 H, CC6H5, β-H), 7.04 (m, 2 H, CC6H5), 7.23–7.55
(m, 30 H, 6 H, PC6H5, CC6H5) ppm. 31P NMR: δ = 38.1 (s, PPh3)
ppm. MS (FAB): m/z (%) = 954 (7) [M]+. C58H46O3P2Ru (954.00):
calcd. C 73.0, H 4.9; found C 73.1, H 4.9.
[Ru(CH=CHC6H4Me-4){O2CCH2CH2(CϵCAuPCy3)}(CO)-
(PPh3)2] (9): To 2 (50 mg, 0.058 mmol) in dichloromethane
(20 mL), a few drops of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)
were added. [AuCl(PCy3)] (29.7 mg, 0.058 mmol) was added, and
the mixture was stirred in the dark overnight. Ethanol (20 mL) was
added, and a yellow solid was obtained by slow concentration un-
der reduced pressure with a rotary evaporator. To increase the
yield, the solution (with precipitate) was kept at –20 °C for 2 h,
and then the product was collected by filtration, washed with cold
ethanol (5 mL) and hexane (10 mL) and dried under vacuum. The
product was slightly soluble in ethanol, which resulted in a moder-
[Ru(CH=CHC5H4FeC5H5)(O2CCH2CH2CϵCH)(CO)(PPh3)2] (5):
The same procedure was followed as that for 2 with pentynoic acid
(13.5 mg, 0.138 mmol), NaOMe (22.4 mg, 0.415 mmol) and
[Ru(CH=CHC5H4FeC5H5)Cl(CO)(BTD)(PPh3)2]
(130 mg,
0.125 mmol) in methanol (10 mL) and dichloromethane (10 mL) to
yield a yellow product (114 mg, 95%). IR (CH Cl ): ν = 2122
˜
2
2
(νCϵC), 1919 (νCO), 1529 (νOCO) cm–1. IR (KBr/Nujol): ν = 2145
˜
(νCϵC), 1909 (νCO), 1520 (νOCO) cm–1. 1H NMR: δ = 1.13, 1.42
(mϫ2, 2ϫ2 H, CH2), 1.66 (t, JH,H = 2.6 Hz, 1 H, CCH), 3.46,
3.79 (sϫ2, 2ϫ2 H, C5H4), 3.73 (s, 5 H, C5H4), 5.51 (d, JH,H
=
15.7 Hz, 1 H, β-H), 7.18 (dt, JH,H = 15.7 Hz, JH,P = 2.3 Hz, 1 H,
α-H), 7.36–7.47 (m, 30 H, C6H5) ppm. 31P NMR: δ = 37.2 (s, PPh3)
ppm. MS (FAB): m/z (%) = 961 (1) [M]+, 722 (3) [M – vinyl –
CO]+. C54H46FeO3P2Ru (961.80): calcd. C 67.4, H 4.8; found C
67.6, H 4.9.
ate yield, yield 50 mg (64%). IR: ν = 2047 (νCϵC), 1915 (νCO), 1646,
˜
1
1575, 1521 (νOCO), 1319, 830 cm–1. H NMR (CD2Cl2): δ = 1.15,
1.30 (mϫ2, 2ϫ2 H, CH2), 1.42–2.04 (m, 33 H, Cy), 2.20 (s, 3 H,
CH3), 5.81 (d, JH.H = 15.6 Hz, 1 H, β-H), 6.36, 6.80 (AB, JA.B
7.8 Hz, 4 H, C6H4), 7.28–7.75 (m, 30 H, C6H5), 7.74 (dt, JH.H
=
=
16.6 Hz, 1 H, α-H, JH,P not resolved) ppm. 31P NMR: δ = 37.7 (s,
RuPPh3), 56.4 (s, AuPCy3) ppm. MS (FAB): m/z (%) = 1344 (1)
[M]+. C69H76AuO3P3Ru (1344.32): calcd. C 61.7, H 5.7; found C
61.8, H 5.6.
[Os(CH=CHC6H4Me-4)(O2CCH2CH2CϵCH)(CO)(PPh3)2] (6):
The same procedure was followed as that for 2 with pentynoic acid
(20.9 mg, 0.213 mmol), NaOMe (34.5 mg, 0.639 mmol) and
[Os(CH=CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2]
(200 mg,
0.194 mmol) in methanol (20 mL) and dichloromethane (20 mL) to
[Ru(CH=CHtBu)(O2CCH2CH2CC{Co2(CO)6}H)(CO)(PPh3)2]
(10): A suspension of 3 (100 mg, 0.120 mmol) and [Co2(CO)8]
(61.5 mg, 0.180 mmol) was stirred in hexane (10 mL) at room tem-
perature under nitrogen for 2 h. The reaction mixture changed from
yellow to brown. All volatiles were removed, and ethanol (10 mL)
was added to the residue. A brown solid was obtained by ultrasonic
trituration. The solid was collected by filtration, washed with cold
ethanol (10 mL) and hexane (10 mL) and dried under vacuum,
yield a reddish brown product (119 mg, 64%). IR (CH Cl ): ν =
˜
2
2
2019 (νCϵC), 1901 (νCO), 1542 (νOCO) cm–1. IR (KBr/Nujol): ν =
˜
2016 (νCϵC), 1903 (νCO), 1549 (νOCO) cm–1. 1H NMR: δ = 1.13,
1.39 (mϫ2, 2ϫ2 H, CH2), 1.67 (t, JH,H = 2.7 Hz, 1 H, CCH), 2.19
(s, 3 H, CH3), 5.58 (d, JH,H = 15.8 Hz, 1 H, β-H), 6.25, 6.77 (AB,
JA,B = 7.9 Hz, 4 H, C6H4), 7.16–7.62 (m, 30 H, C6H5), 7.97 (dt,
JH,H = 15.8 Hz, JH,P = 2.1 Hz, 1 H, α-H) ppm. 31P NMR: δ = 19.0
(s, PPh3) ppm. MS (ES+): m/z (%)
=
958 (77) [M]+.
yield 62 mg (46%). IR (CH Cl ): ν = 2091, 2051, 2023 (νCoCO),
˜
2
2
1941 (νRuCO), 1534 (νOCO) cm–1. IR (KBr/Nujol): ν = 2089, 2049,
C51H44O3OsP2·0.75CH2Cl2 (1020.77): calcd. C 60.9, H 4.5; found
C 60.8, H 4.5.
˜
1
2024 (νCoCO), 1915 (νRuCO), 1552 (νOCO) cm–1. H NMR: δ = 0.72
(s, 9 H, Bu), 1.09, 2.00 (mϫ2, 2ϫ2 H, CH2), 5.13 (d, JH,H
=
[{RuCl(O2CCH2CH2CϵC)(CO)(PPh3)2}2]
(7):
[RuCl(CO)-
15.3 Hz, 1 H, β-H), 5.71 (s, 1 H, CCH), 6.62 (br d, JH,H = 15.3 Hz,
(O2CCH2CH2CϵCH)(PPh3)2] (100 mg, 0.127 mmol), [PdCl2-
(PPh3)2] (44.6 mg, 0.064 mmol), CuI (5 mg, 0.026 mmol) and NEt3
(5 drops) were stirred in dichloromethane (10 mL) and methanol
(10 mL) at room temperature for 2 h. Slow concentration under
reduced pressure provided a light brown product, which was col-
lected by filtration, washed with ethanol (20 mL) and hexane
1 H, α-H), 7.35–7.49 (m, 30 H, C6H5) ppm. 31P NMR: δ = 35.6 (s,
PPh3) ppm. MS (MALDI): m/z (%)
=
1120 (20) [M]+.
C54H46Co2O9P2Ru (1119.84): calcd. C 57.9, H 4.1; found C 57.4,
H 3.9.
X-ray Crystallography: Crystals of 2 and 3 were grown by slow
diffusion of ethanol into dichloromethane solutions of the com-
plexes. The single-crystal X-ray diffraction data for 2 and 3 were
collected by using graphite-monochromated Mo-Kα radiation (λ =
(10 mL) and dried under vacuum, yield 78 mg (76%). IR: ν = 2163
˜
(νCϵC), 1942 (νCO), 1513 (νOCO) cm–1. 1H NMR (CD2Cl2): δ =
1.00, 1.34 (tϫ2, JH,H = 8.0 Hz, 2ϫ4 H, CH2), 7.32–7.80 (m, 60
H, C6H5) ppm. 31P NMR (CD2Cl2): δ = 35.0 (s, PPh3) ppm. MS 0.71073 Å) with an Enraf–Nonius KappaCCD diffractometer
Eur. J. Inorg. Chem. 2014, 2065–2072
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FULL PAPER
equipped with a Cryostream N2 open-flow cooling device[33] at
150(2) K. Series of ω-scans were performed in such a way as to
cover a sphere of data to a maximum resolution of 0.77 Å. The cell
parameters and intensity data for 2 and 3 were processed by using
the DENZO-SMN package,[34] and the structures were solved by
direct methods and refined by full-matrix least-squares on F2 by
using the SHELXTL software.[35] Intensities were corrected for ab-
sorption effects by the multiscan method based on multiple scans
of identical and Laue equivalent reflections (by using the SORTAV
software).[36]
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[2]
[3]
[4]
Non-hydrogen atoms were refined with anisotropic displacement
parameters except for the disordered atoms of the pentynoate li-
gands. The crystal data and structure refinement parameters are
included in Table 2.
Table 2. Crystal data for complexes 2 and 3.
2
3
Chemical formula
Fw
Crystal system
Crystal colour
Crystal size [mm]
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C51H44O3P2Ru
867.93
triclinic
C48H46O3P2Ru
833.91
triclinic
yellow
yellow
0.25ϫ0.14ϫ0.08 0.16ϫ0.10ϫ0.04
¯
¯
P1
P1
12.0476(1)
13.1275(2)
17.1458(2)
89.1754(7)
70.4941(7)
69.2626(5)
2373.82(5)
2
1.214
150(2)
0.436
896
12.2430(1)
13.1912(1)
14.6561(2)
105.1013(4)
105.0422(5)
100.4722(5)
2126.52(4)
2
1.302
150(2)
0.483
864
[5]
[6]
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γ [°]
V [Å3]
Z
Dcalcd. [g/cm3]
T [K]
[7]
μ(Mo-Kα) [mm–1]
F(000)
Reflections collected
Unique reflections (Rint
R1 [IϾ2σ(I)]
wR2 (all data)
39162
10705 (0.040)
0.0489
45608
9564 (0.051)
0.0448
[8]
)
[9]
0.0658
0.0591
[10]
For an overview of vinyl chemistry of ruthenium(II), see: a)
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CCDC-956685 (for 2) and -956686 (for 3) 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.
Supporting Information (see footnote on the first page of this arti-
cle): ORTEP plots for 2 and 3, details of the molecular weight
determination by the Signer method.
[11]
[12]
Acknowledgments
The authors thank Johnson Matthey Ltd. for a generous loan of
ruthenium and osmium salts.
[1] a) J. D. E. T. Wilton-Ely, D. Solanki, G. Hogarth, Eur. J. Inorg.
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Received: November 28, 2013
Published Online: March 10, 2014
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