Structural studies of some compounds containing C2 fragments attached to various metal-ligand end-groups

Article abstract of DOI:10.1002/zaac.201100099

The preparation, characterisation and single-crystal XRD molecular structure determinations of four complexes containing -CC-ML_n end-groups, namely Ru{C≡CFc′(I)}(dppe)Cp (1), the vinylidene [Os(=C=CH₂)(PPh₃)₂Cp]

Full text of DOI:10.1002/zaac.201100099

ARTICLE
DOI: 10.1002/zaac.201100099
Structural Studies of Some Compounds Containing C2 Fragments Attached
to Various Metal-Ligand End-Groups
Michael I. Bruce,*[a] Maryka Gaudio,[a] Benjamin C. Hall,[a] Brian K. Nicholson,[b]
Gary J. Perkins,[a] Brian W. Skelton,[c] and Allan H. White[c]
Keywords: C2 ligands; Metal complexes; XRD structure; Ruthenium; Osmium; Platinum
Abstract. The preparation, characterisation and single-crystal XRD range of –CC– environments is found, extending from the σ-bonded
molecular structure determinations of four complexes containing –CC– alkynyl group in 1 to examples where the C2 unit interacts with either
MLn end-groups, namely Ru{C≡CFc'(I)}(dppe)Cp (1), the vinylidene a proton (in vinylidene 2), by bridging a dicobalt carbonyl moiety (in
[Os(=C=CH2)(PPh3)2Cp]PF6
(2),
trans-Pt(C≡CC6H4-4-C≡CPh)- 3) or the AuRu3 cluster in 4. Changes in geometry are rationalised by
{C≡CC6H4-4-C2Ph[Co2(μ-dppm)(CO)4]}(PPh3)2 (3), and C6H4{μ3-C2- considering the various bonding modes.
[AuRu3(CO)9(PPh3)]}2-1,4 (4) are reported. In these compounds a
further comment. The formulas of compounds 1–4 are shown
in Scheme 1.
Introduction
The chemistry of metal complexes containing alkynyl and
polyynyl groups attached to metal-ligand centres has interested
us for many years.[1] During the course of this work, several
related complexes, which contain a range of different MLn end-
groups, have been obtained and their molecular structures have
been determined by single-crystal XRD techniques. Common
features include a –C≡C– or =C=C= fragment bonded to a
metal atom, together with, in some cases, instances where a C2
group interacts with a bi- or tri-metallic centre via the alk-
ynyl π bonds. The molecular structure determinations of four
of these compounds are collected in this paper, together with
brief details of their syntheses, properties and significance.
Results
Syntheses and Properties
Most compounds have been characterised by elemental anal-
yses and from their spectroscopic properties, including IR,
NMR and electro-spray (ES) mass spectrometry. Characteristic
NMR resonances for the MLn fragments are found. The details
are listed in the Experimental Section and only specific details
relating to the organic ligand fragment will be the subject of
* Prof. Dr. M. I. Bruce
Scheme 1.
Fax: + 61 8 8303 4358
E-Mail: michael.bruce@adelaide.edu.au
[a] School of Chemistry and Physics
University of Adelaide
Adelaide, South Australia 5005
[b] Department of Chemistry
University of Waikato
Ru{C≡CFc('I})(dppe)Cp (1)
As for the ferrocenyl analogue FcC≡CSiMe3,[2] the reaction
between (Me3SiC≡C)Fc'(I) [Fc' = ferrocene-1,1'-diyl, Fe(η-
C5H4-)2] and RuCl(dppe)Cp was carried out in MeOH in the
Hamilton, New Zealand
[c] Chemistry M313, SBBCS
University of Western Australia
Crawley, Western Australia 6009
Z. Anorg. Allg. Chem. 2011, 637, 1207–1212
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M. I. Bruce et al.
ARTICLE
presence of KF and afforded Ru{C≡CFc'(I)}(dppe)Cp (1) in CO groups from each cluster to give 1,4-C6H4{μ3-
34 % yield. Characteristic resonances for the Fc' group were C2[AuRu3(CO)9(PPh3)]}2 (4). The formulation was initially
found in the NMR spectra, whereas the IR ν(C≡C) band ap- confirmed by elemental microanalysis and by its spectroscopic
peared at 2079 cm–1. The –C≡C–Ru(dppe)Cp fragment properties, including five terminal ν(CO) bands between 2070
showed appropriate resonances including Cp at δH 4.70, δC and 1991 cm–1 in the IR spectrum and singlet signals at δC
83.17 and a triplet for Cα at δC 109.68, whereas the ES-MS 224.80 for the CO groups and δP 61.9 for Au(PPh3) in the
contained [M + H]+ at m/z 901, confirmed by a high-resolution NMR spectra. The ES-MS contains ions at m/z 2177 and 1695,
measurement.
which are assigned to [M + Na]+ and [M – Au(PPh3)]+, respec-
tively. This complex is another example of a μ3-alkynyl-Ru3
system, in which the Au(PPh3) replaces the more familiar H
ligand, with which it is isolobal.[8]
[Os(=C=CH2)(PPh3)2Cp]PF6 (2)
Protonation of Os(C≡CH)(PPh3)2Cp occurs at the electron-
rich Cβ atom to give vinylidene [Os(=C=CH2)(PPh3)2Cp]PF6
(2) in a reaction that can be easily reversed by addition of base,
such as NaOMe.[3–5] Although many examples of this type of
reaction are known, the parent complex in the osmium series
has now been made efficiently from the direct reaction be-
tween OsCl(PPh3)2Cp, HC≡CSiMe3 and [NH4]PF6 in ButOH
under reflux. Characteristic spectroscopic properties include =
CH2 and Cp resonances at δH 2.11 and 5.38, δC 98.02 and
93.14, respectively, the Os=C singlet at δ = 306.74, and the
PPh3 singlet at δP –0.4 in the NMR spectra, together with the
molecular cation at m/z 807. Deprotonation (KOBut in thf) af-
fords Os(C≡CH)(PPh3)2Cp in 83 % yield.
Molecular Structures
Plots of the four molecules 1–4 are given in Figure 1, Fig-
ure 2, Figure 3, and Figure 4, with selected bond parameters
given in the captions thereto.
trans-Pt(C≡CC6H4C≡CPh){C≡CC6H4C2Ph[Co2(μ-
dppm)(CO)4]}(PPh3)2 (3)
Coordination of the dicobalt carbonyl fragment Co2(CO)6 to
alkynes is a useful method of protecting the latter group during
other reactions.[6] More recently, the use of the dppm-substi-
tuted precursor Co2(μ-dppm)(CO)6 has given derivatives
which are considerably more stable than those obtained from
Co2(CO)8.[7] Extension of this reaction to the bis-alkynyl trans-
Pt(C≡CC6H4C≡CPh)2(PPh3)2 results in addition of one or two
Co2 fragments to the outer C≡C triple bond(s) of the alkynyl
groups, no doubt the result of severe steric hindrance around
the inner C≡C triple bond produced by the two PPh3 ligands
attached to platinum. The two products are readily separated
by preparative TLC and can be distinguished by their 31P NMR
spectra, signals at δ = 19.8 (PPh3) and 38.4 (dppm) in both
complexes having relative intensities 1:1 and 1:2, respectively.
The former resonance shows J(PPt) ca. 2650 Hz characteristic
of the trans conformation. In the ES-MS, ions at m/z 1737 and
2351, respectively, are assigned to [M + H]+. X-ray quality
crystals of marginal quality were obtained only for the mono
adduct 3, presented here. In addition to allowing the composi-
tion and structure of this complex to be confirmed, there is
also an opportunity of comparing both complexed and free
C≡C triple bonds in the same environment.
Figure 1. Plot of the major component of Ru{C≡CFc'(I)}(dppe)Cp (1).
Ru–P(1,2) 2.2419, 2.2534(7), Ru–C(cp) 2.230–2.251(3), av. 2.241, Fe–
C(cp) 2.022(7)–2.10(3), Ru–C(1) 2.020(3), C(1)–C(2) 1.185(4), C(2)–
C(201) 1.474(10), C(200)–I(200) 2.076(5) Å. P(1)–Ru–P(2) 84.45(3),
P(1,2)–Ru–C(1) 81.85, 88.50(8), Ru–C(1)–C(2) 177.2(3), C(1)–C(2)–
C(201) 172.9(11)°.
Ru{C≡CFc'(I})(dppe)Cp (1)
The structure of 1 is very similar to that of the unsubstituted
Ru(C≡CFc)(dppe)Cp,[2] there being no significant differences
in the bond parameters of the formally octahedral Ru(PP)Cp
end-group [Ru–P(1,2) 2.2419, 2.2534(7) Å, P(1)–Ru–P(2)
84.45(3), P(1,2)–Ru–C(1) 81.85, 88.50(8)°], except for the di-
vergence of the latter pair of angles. In the parent complex and
other similar fragments described in ref.[2] these angles vary
widely over ca. 10° and are presumably easily susceptible to
1,4-C6H4{μ3-C2[AuRu3(CO)9(PPh3)]}2 (4)
The bis-alkyne 1,4-C6H4{C≡C[Au(PPh3)]}2 reacts with two various lattice forces. The Ru–C(1) and C(1)–C(2) separations
equiv. Ru3(CO)10(NCMe)2 by oxidative addition of each Au– are 2.020(3) and 1.185(4) Å, respectively, consistent with the
C bond to the cluster with concomitant interaction of the C≡C alkynyl–metal formulation shown. The C(200)–I(200) bond
triple bonds with two Ru3 clusters and displacement of three [2.076(5) Å] is unique to this compound.
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Compounds with C2 Fragments Attached to Metal-Ligand End-Groups
Figure 4. Plot of a centrosymmetric molecule of 1,4-C6H4{μ3-
C2[AuRu3(CO)9(PPh3)]}2 (4). Au(1)–Ru(1,2) 2.758, 2.777(2), Ru(1)–
Ru(2,3) 2.845, 2.841(2), Ru(2)–Ru(3) 2.832(2), Au(1)–P(1) 2.296(5),
Ru(1)–C(1,2) 2.20, 2.24(2), Ru(2)–C(1,2) 2.20, 2.23(2), Ru(3)–C(1)
1.96(2), C(1)–C(2) 1.28(2), C(2)–C(3) 1.48(2) Å. P(1)–Au(1)–Ru(1,2)
147.1, 151.0(1), Ru(1)–Au(1)–Ru(2) 61.86(5), Ru(1)–C(1,2)–Ru(2)
80.7, 79.0(5), Ru(3)–C(1)–C(2) 154.5(2), C(1)–C(2)–C(3) 141.3(2)°.
Figure 2. Plot of cation 1 in [Os(=C=CH2)(PPh3)2Cp]PF6 (2). Across
both cations (n = 1, 2), Os–P are 2.320–2.354(5), Os–C(cp) 2.25–
2.30(2), av. 2.27, Os–C(n1) 1.868(12), 1.839(11), C(n1)–C(n2)
1.30(2) Å (× 2), P–Os–P 98.18, 98.50(13), P–Os–C(n1) 90.5–96.8(4),
Os–C(n1)–C(n2) 169.7, 171.4(10)°.
[1.30(2) Å (× 2)] are indicative of a C=C double bond. The
bond parameters fall in the usual range observed previously for
Ru-vinylidene complexes, including Ru(=C=CH2)(PPh3)2Cp*
[Ru–P, 2.362, 2.355(2), Ru–C 1.843(5), C(1)–C(2)
1.297(8) Å],[9] as expected from the closely similar ruthenium
and osmium atomic radii. In Os(C≡CH)(dppe)Cp*,[1c] Os–
C(CH) are 2.017, 2.043(8) Å and Os–P 2.258–2.265(2) Å, the
latter being appreciably shorter than the present, which results
from the positively charged osmium atom; the P–Os–P angles
are 82.68, 82.88(7)°.
trans-Pt(C≡CC6H4C≡CPh){C≡CC6H4C2Ph[Co2(μ-
Figure 3.
Plot
of
a
molecule
of
trans-
dppm)(CO)4]}(PPh3)2 (3)
Pt(C≡CC6H4C≡CPh){C≡CC6H4C2Ph[Co2(μ-dppm)(CO)4]}(PPh3)2 (3).
Pt–P(3,4) 2.279, 2.266(5), Co(1)–P(1) 2.222(5), Co(2)–P(2) 2.224(5),
Pt–C(1,5) 1.99, 2.02(2), Co(1)–C(3,4) 1.97, 1.94(2), Co(2)–C(3,4)
1.91, 1.96(2), C(1)–C(2) 1.20(2), C(3)–C(4) 1.37(3), C(5)–C(6)
1.21(3), C(7)–C(8) 1.15(3) Å. P(3)–Pt–P(4) 176.6(2), P(3)–Pt–C(1,5)
94.0, 83.1(5), P(4)–Pt–C(1,5) 87.7, 95.0(5), C(1)–Pt–C(5) 174.5(7),
Pt–C(1)–C(2) 175(2), Pt–C(5)–C(6) 173(2), C(1)–C(2)–C(201) 173(2),
C(4)–C(3)–C(204) 140(2), C(3)–C(4)–C(401) 138(2), C(5)–C(6)–
C(601) 174(2), C(8)–C(7)–C(604) 168(2), C(7)–C(8)–C(801) 176(2)°.
The
molecular
structure
of
trans-Pt(C≡CC6-
H4C≡CPh)2(PBu3)2 has been reported on an earlier
occasion.[10] The structure determination of the closely related
derivative 3, in which the PPh3 ligands have replaced PBu3,
confirms the trans square-planar geometry expected for the
platinum atom, with Pt–P(3,4) [2.279, 2.266(5) Å] and Pt–C
[1.99, 2.02(2) Å] bond lengths falling within the usual ranges.
Of interest is the close similarity between the two Pt–C≡C
fragments, the Co2(μ-dppm)(CO)4 fragment having little influ-
ence. However, considering the outer C≡C triple bonds, C(7)–
[Os(=C=CH2)(PPh3)2Cp]PF6 (2)
In this structure, two independent molecules, devoid of crys- C(8) [1.15(3) Å] is normal, whereas C(3)–C(4) [1.37(3) Å] is
tallographic symmetry, comprise the asymmetric unit. The os- considerably lengthened and consistent with extensive back-
mium atom in the cation of 2 (cation 1 is depicted in Figure 2) bonding from the two cobalt atoms into the C≡C π* orbitals.
is also formally octahedral, with the usual facially-bonded Cp This also has the effect of distorting the C≡C fragment from
group [Os–C(cp) av. 2.27 Å] supplemented by two PPh3 li- linearity, with angles at C(3, 4) in the C(204)–C(3)–C(4)–
gands [Os–P 2.320–2.354(5) Å] and the vinylidene ligand with C(401) chain being 137(1), 140(2)° [cf. angles at C(7, 8) 168,
angles P–Os–P 98.18, 98.50(13), P–Os–C(n1) 90.5–96.8(4)°. 176(2)°]. In the PBu3 complex mentioned above, the analogous
The short Os=C bonds [Os–C(1) 1.868(12), 1.839(11) Å] sup- C≡C triple bonds are 1.214(2) (inner), 1.199(2) Å (outer), with
port the multiple bond character indicated by the downfield 13
C
Pt–C 1.996(2) Å. The Co2(μ-dppm)(CO)4 fragment has bond
chemical shift (δC ca. 306), while the long C(1)–C(2) bonds parameters [Co–Co 2.464(4), Co–P 2.222, 2.224(5), Co–C
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M. I. Bruce et al.
ARTICLE
1.91–1.97(2) Å] within the normal ranges found for earlier ex- [C(4)–C(3)–C(204) 140(2), C(3)–C(4)–C(401) 138(2)°] results
amples of Co2(μ-alkyne)(μ-dppm)(CO)4 complexes, cf., Co2(μ- from “rehybridisation” of these carbons.
HC2Ph)(μ-dppm)(CO)4 [Co–Co 2.4858(4), Co–P 2.2330,
In 4, oxidative addition of the acetylenic C–H bond to the
2.2244(5), Co–C 1.947–1.974(2), C(1)–C(2) 1.350(2) Å].[11,12] Ru3 cluster has occurred to give an Ru(3)–C(1) σ bond
It is notable that there is considerable distortion along the [1.96(2) Å], which is not significantly different from a normal
chain of 13 atoms –C(3)–…–Pt–…–C(801)– (sum of devia- Ru–C(sp) bond, while the C(1)≡C(2) fragment is also π bonded
tions from 180° = 47°, neglecting the C6 rings), possibly result- to Ru(1,2). This results in lengthening of the C≡C triple bond
ing from lattice forces and the small bending moments of the to 1.28(2) Å and bending at each carbon of 154.5(2),
constituent bonds.[13]
141.3(2) Å°, respectively, similar to that found for 3, but with
a trans conformation.
In conclusion, these studies have demonstrated the effects on
the parent alkynyl–metal system of protonation and coordina-
tion of the C≡C triple bond to bi- and trimetallic systems,
whereby the initially linear M–C(sp)–C(sp)– moiety progres-
sively adopts a bent conformation with concomitant lengthen-
ing of the C–C bond, consistent with a formal rehybridisation
of the two carbons from C(sp) to C(sp2).
1,4-C6H4{μ3-C2[AuRu3(CO)9(PPh3)]}2 (4)
Coordination of the C≡C triple bond to the Ru3 clusters in 4
has the effect of increasing the back-bonding into this group
from the cluster, so that the CC separation is now lengthened
to 1.28(2) Å. Angles at C(1) and C(2) in the Ru(3)–C(1)–
C(2)–C(3) moiety are now 154.5, 141.3(2)°. The Ru–Ru dis-
tances are similar to those found in other clusters of this type,
although the Au(PPh3) group which spans the Ru(1)–Ru(2)
bond does not produce any significant lengthening of this Ru–
Ru bond compared with the other two. This feature thus con-
trasts with the usual lengthening of a M–M bond when bridged
by the isolobal hydrogen atom. Other bond parameters are sim-
ilar to those found in other examples of complexes of this type,
e.g., AuRu3(μ3-C2R)(CO)9(PPh3) (R = But,[14] C6H4C≡CC6H4X
(X = Me, CO2Me, OMe, NO2, CN)[15]).
Experimental Section
General: Experimental details and instrumentation were similar to
those reported in an earlier paper from our group.[17]
Reagents: The compounds Fe(η-C5H4I)2,[18] trans-Pt(C≡CC6H4-
C≡CPh)2(PPh3)2,[19] OsCl(PPh3)2Cp,[20] 1,4-C6H4{C≡CAu(PPh3)}2
[21]
were made by the cited methods.
Synthesis of Ru{C≡CFc'(I)}(dppe)Cp (1)
Discussion
(a) (Me3SiC≡C)Fc'(I): To a degassed stirring solution of Fc'(η-
C5H4I)2 (1.19g, mmol) and HC≡CSiMe3 (1.0 mL, mmol) in NHPri2
(25 mL) in a pressure Schlenk tube was added Pd(OAc)2 (20 mg,
mmol), CuI (16 mg, mmol) and PPh3 (72 mg, mmol) and the resulting
mixture was stirred for 30 min before being sealed and heated to 90 °C
for 16 h. The cooled solution was diluted with diethyl ether and the
mixture filtered and washed with diethyl ether until no further colour
leached from the solid mass. The solvent was removed in vacuo and
the crude residue purified by column chromatography (silica gel, gradi-
The reference separation for a C(sp)–C(sp) triple bond is
1.2033(2) Å in C2H2.[13]. When a C≡C triple bond is σ-bonded
to a transition metal, there is no significant shortening, as the
interaction consists of a filled–filled interaction between the
metal d orbitals and the C≡C π orbitals.[16]. This contrasts with
the situation in an M–CO bond, where the M–C bond length
is found to be significantly shorter. In 1, the Ru–C(1) separa-
tion is 2.020(3) Å, with C(1)–C(2) 1.185(4) Å, in accord with
theory. However, electron density accumulates on Cβ, this atom
becoming electron-rich and therefore being susceptible to elec-
trophilic attack.
In 2, as a result, addition of a proton to Cβ results in electron
density being removed from the C≡C bond to the Os–Cα bond,
which is shorter than the normal Os–C(sp) bond. The Cα=Cβ
separation lengthens, so that the overall representation of this
complex involves an Os=C=C fragment, or a vinylidene. The
experimental lengths are Os=C 1.92(2), 1.79(2), C=C 1.32(3),
1.30(2) Å, as expected.
The platinum complex 3 contains four C≡C triple bonds, one
“outer” at 1.15(3) Å, two “inner”, bonded to the platinum atom
at 1.20(2), 1.21(3) Å, and one also attached to the Co2(μ-
dppm)(CO)4 group, at 1.37(3) Å. Whereas the precision of the
determination does not allow a detailed discussion of the non-
π-coordinated C≡C bonds, it is clear that there is not any sig-
nificant lengthening. However, interaction of the π electron
density of C(3)≡C(4) with the dicobalt fragment results in sig-
nificant back-bonding from the metal atoms to and resulting
ent hexane to 20 % dichloromethane
/
hexane) to afford
(Me3SiC≡C)Fc'(I) as an orange oil and Fc'(η-C5H4C≡CSiMe3)2, also
an orange oil.
(b) Ru{C≡CFc'(I)}(dppe)Cp (1):
A
mixture containing
RuCl(dppe)Cp (118 mg, 0.197 mmol), (Me3SiC≡C)Fc'(I) (73 mg,
0.24 mmol), KF (29 mg, 0.50 mmol) and dbu (1 drop) was heated in
MeOH (20 mL) under reflux for 1 h. The solvent was removed in
vacuo and the crude residue extracted with benzene. The solution vol-
ume was reduced and subjected to column chromatography (basic alu-
mina, gradient elution hexane to benzene) to afford
Ru{C≡CFc'(I)}(dppe)Cp 1 (60 mg, 34 %) an orange solid. X-ray qual-
ity crystals from Et2O / hexane. Anal. Calcd (C43H37FeIP2Ru): C,
57.42; H, 4.15 %; M, 900. IR (Nujol): ν = (C≡C) 2079m cm–1. 1H
˜
NMR (C6D6) δ = 2.13–2.26, 2.69–2.81 (2 x m, 4 H, dppe), 3.62–3.63
(m, 2 H, C5H4), 3.82 (s, 4 H, C5H4), 3.96–3.98 (m, 2 H, C5H4), 4.70
(s, 5 H, Cp), 6.96–6.97 (m, 7 H, Ph), 7.20–7.29 (m, 9 H, Ph), 8.04–
8.10 (m, 4 H, Ph). 13C NMR (C6D6): δ = 28.82–29.43 (m, CH2), 41.39,
70.14, 70.22, 70.82, 70.93, 73.38, 73.49, 76.04, 76.12, 78.74, 83.17
(Ru–Cp), 106.18, 109.68 [t, J(C,P) = 25.5 Hz, Cα], 129.16, 130.06,
131.96–132.09 (m), 135.21–135.33 (m), 137.37–138.17 (m), 143.50–
144.25 (m). 31P NMR (C6D6): δ = 87.30. ES-MS (m/z): 901, [M +
lengthening of this bond. In addition, bending at C(3) and C(4) H]+. HR-MS: [M + H]+ 901.0015 (calcd. 900.9886).
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Compounds with C2 Fragments Attached to Metal-Ligand End-Groups
faster
moving
major
band
contained
trans-
Synthesis of [Os(= C=CH2)(PPh3)2Cp]PF6 (2)
Pt(C≡CC6H4C≡CPh){C≡CC6H4C2Ph[Co2(μ-dppm)(CO)4]}(PPh3)2
3
A suspension of OsCl(PPh3)2Cp (100 mg, 0.12 mmol), [NH4]PF6
(37.5 mg, 0.25 mmol) and HC≡CSiMe3 (58.9 mg, 0.6 mmol) was
heated in ButOH (15 mL) under reflux for 4 h to give a clear solution.
After cooling, solvent was removed and the residue was taken up in
the minimum amount of CH2Cl2 and filtered through a cotton-wool
plug into rapidly stirred Et2O to give a yellow precipitate of [Os(= C=
CH2)(PPh3)2Cp]PF6 2 (70 mg, 62 %). Anal. Calcd (C43H37F6OsP3): C,
54.32; H, 3.92 %; M, 807. Found: C, 54.37; H, 3.98 %. 1H NMR
([D6]acetone): δ = 2.11 (br. m, 2 H, CH2), 5.38 (s, 5 H, Cp), 7.22–
7.49 (m, 30 H, Ph). 13C NMR ([D6]acetone): δ = 93.14 (Cp), 98.02
(71 mg, 45 %; Rf = 0.40), identified by ES-MS (MeOH + NaOMe, m/
z): 1760, [M + Na]+; 1737, [M + H]+ (calcd. M, 1736). 1H NMR
(CDCl3): δ = 6.92–7.86 (m, Ph + C6H4). 31P NMR (CDCl3): δ = 19.8
[t, J(PPt) = 2644 Hz, PPh3], 38.4 (s, dppm). The lower band (Rf =
0.35) contained trans-Pt{C≡CC6H4C2Ph[Co2(μ-dppm)(CO)4]}2(PPh3)2
(50 mg, 23 %), ES-MS (m/z): 2375, [M + Na]+; 2351, [M + H]+ (calcd.
1
M, 2350). H NMR (CDCl3): δ = 6.97–7.89 (Ph + C6H4). 31P NMR
(CDCl3): δ = 19.8 [t, J(PPt) = 2653 Hz, 1P, PPh3], 38.4 (s, 2P, dppm).
(Cβ), 129.33–136.12 (Ph), 306.74 (s, Os
=
C). 31P NMR
Synthesis of 1,4-C6H4{μ3-C2[AuRu3(CO)9(PPh3)]}2 (4)
([D6]acetone): δ = –0.36 (s, PPh3), –141.85 [sept, J(PF) = 706 Hz,
PF6]. ES-MS (MeOH, m/z): 807, [Os(CCH2)(PPh3)2Cp]+.
1,4-C6H4{C≡C[Au(PPh3)]}2 (40.6 mg, 0.039 mmol) was added to a
solution of Ru3(CO)10(NCMe)2 [prepared from Ru3(CO)12 (50 mg,
0.078 mmol) and Me3NO (12 mg, 0.16 mmol) in CH2Cl2 (15 mL) and
MeCN (5 mL) at –10 °C]. On warming slowly to room temp., the
colour darkened and after stirring a further 2 h, preparative TLC (ace-
Deprotonation of [Os(= C=CH2)(PPh3)2Cp]PF6 (50 mg, 0.05 mmol)
with KOBut (6.7 mg, 0.06 mmol) in thf (10 mL), followed after
30 min by removal of solvent and extraction of the residue with C6H6
until colourless and evaporation of the filtered extract afforded yellow
tone-hexane,
3/7)
enabled
separation
of
1,4-C6H4{μ3-
Os(C≡CH)(PPh ) Cp (33 mg, 83 %). IR (nujol): ν = (≡CH) 3284s,
˜
C2[AuRu3(CO)9(PPh3)]}2 4 (26 mg, 15 %; Rf = 0.37). Anal. Calcd
(C64H34Au2O18P2Ru6): C, 36.22; H, 1.61 %; M, 2154. Found: C, 36.30;
H, 1.70 %. IR (cyclohexane): ν(CO) 2070m, 2040s, 2013m, 1997s,
3 2
1
ν(C≡C) 1929w cm–1. H NMR (C6D6): δ = 2.42 (br., 1 H, ≡CH), 4.45
(s, 5 H, Cp), 6.94–7.71 (m, 30 H, Ph). 13C NMR (C6D6): δ = 82.13
(Cp), 95.31 (Cβ), 127.59–140.17 (Ph). 31P NMR (C6D6): δ = 2.3
(PPh3).
1
1991 (sh) cm–1. H NMR (C6D6): δ = 6.90–7.56 (m, 30 H, Ph), 7.53
(s, 4 H, C6H4). 31P NMR (C6D6): δ = 61.9 [s, Au(PPh3)]. ES-MS
(MeOH + NaOMe, m/z): 2177, [M + Na]+; 1695, [M – Au(PPh3)]+.
Synthesis of trans-Pt(C≡CC6H4C≡CPh){C≡CC6H4C2Ph[Co2(μ-
dppm)(CO)4]}(PPh3)2 (3)
Structure Determinations
A mixture of trans-Pt(C≡CC6H4C≡CPh)2(PPh3)2 (100 mg, 0.9 mmol) Full spheres of diffraction data were measured using a Bruker AXS
and Co2(μ-dppm)(CO)6 (120 mg, 0.18 mmol) was heated in benzene CCD area-detector instrument. All data were measured using mono-
(25 mL) under reflux for 16 h. Solvent was removed and the residue chromatic Mo-Kα radiation, λ = 0.71073 Å. Ntot reflections were
was separated by TLC (acetone-hexane 3/7) into several bands. The merged to N unique (Rint cited) after “empirical” / multiscan absorption
Table 1. Crystal data and refinement details.
Complex
1a)
2b)
3c)
4
CCDC #
Formula
MW
811951
811948
811950
811949
C43H37FeIP2Ru
899.49
C43H37OsP2+.F6P–
950.84
C97H70Co2O4P4Pt.CH2Cl2
1821.3
C64H34Au2O18P2Ru6
2153.21
Crystal system
Space group
a /Å
monoclinic
P21/n
11.7456(3)
19.5757(4)
16.4370(4)
orthorhombic
Pca21
27.153(5)
13.043(3)
21.021(4)
monoclinic
P21/c
triclinic
¯
P1
29.746(5)
11.883(3)
12.169(3)
13.031(3)
67.719(3)
82.450(3)
79.460(3)
1710.2(7)
2.091
b /Å
15.843(3)
c /Å
18.689(3)
α /deg.
β /deg.
102.210(2)
102.696(3)
γ /deg.
V /Å3
3693.8(2)
7445(3)
8592(3)
ρc /g·cm–3
Z (f.u.)
1.617
1.697
1.408
4
8
4
1
2θmax /deg.
μ (Mo-Kα) /mm–1
Tmin/max
70
58
50
50
1.75
3.6
2.19
5.7
0.87
0.76
0.78
0.63
Crystal dimensions /mm
Ntot
0.37 × 0.11 × 0.09
71129
0.18 × 0.15 × 0.07
69670
0.38 × 0.04 × 0.04
60486
0.35 × 0.15 × 0.09
14997
N (Rint)
No
R1 [I > 2σ(I)]
wR2 (all data)
T /K
15317 (0.045)
8967
18765 (0.070)
12347
14837 (0.136)
12361
5925 (0.064)
5227
0.048
0.078
0.138
0.092
0.155
0.196
0.31
0.21
200(2)
150(2)
150(2)
150(2)
a) The ferrocene component is disordered over two sets of sites, occupancies refining to 0.7036(9) and complement. b) xabs was 0.018(12). c)
Weak and limited data would support meaningful anisotropic displacement parameter refinement for Pt, Co, P, Cl only. The solvent was modeled
as a pair of fragments, site occupancies 0.5. Phenyl ring geometries were constrained to ideal values.
Z. Anorg. Allg. Chem. 2011, 1207–1212
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1211

M. I. Bruce et al.
ARTICLE
[4] a) A. Davison, J. P. Solar, J. Organomet. Chem. 1978, 155, C8;
b) A. Davison, J. P. Selegue, J. Am. Chem. Soc. 1978, 100, 7763.
[5] a) M. I. Bruce, R. C. Wallis, Aust. J. Chem. 1979, 32, 1471;
b) M. I. Bruce, A. G. Swincer, R. C. Wallis, J. Organomet. Chem.
1979, 171, C5; c) M. I. Bruce, A. G. Swincer, Adv. Organomet.
Chem. 1987, 22, 59.
correction (proprietary software) and used in the full-matrix least-
squares refinements on F2, No with F > 4σ (F) being considered “ob-
served“. Anisotropic displacement parameter forms were refined for
the non-hydrogen atoms, hydrogen atom treatment following a riding
model. Reflection weights were (σ2(Fo ) + (aP)2 (+ bP))–1 where P =
2
2
2
(Fo + 2Fc )/3. Neutral atom complex scattering factors were used
within the SHELXL 97 program.[22] Pertinent results are given in the
figures which show non-hydrogen atoms with 50 % probability ampli-
tude displacement envelopes and hydrogen atoms with arbitrary radii
of 0.1 Å) and in Table 1.
[6] K. M. Nicholas, R. Pettit, Tetrahedron Lett. 1971, 12, 3475.
[7] M. I. Bruce, K. A. Kramarczuk, G. J. Perkins, B. W. Skelton,
A. H. White, N. N. Zaitseva, J. Cluster Sci. 2004, 15, 119.
[8] J. W. Lauher, K. Wald, J. Am. Chem. Soc. 1981, 103, 7648.
[9] Y. Kawata, M. Sato, Organometallics 1997, 16, 1093.
[10] M. I. Bruce, J. Davy, B. C. Hall, Y. Jansen van Galen, B. W.
Skelton, A. H. White, Appl. Organomet. Chem. 2002, 16, 559.
[11] V. Derdau, S. Laschat, I. Dix, P. G. Jones, Organometallics 1999,
18, 3859.
Full details of the structure determinations (except structure factors)
have been deposited with the Cambridge Crystallographic Data Centre
as CCDC-811948, -811949, -811950, -811951. Copies of this informa-
tion may be obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (Fax: +44-1223-336-033; E-
Mail: deposit@ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
[12] T. J. Snaith, P. J. Low, R. Rousseau, H. Puschmann, J. A. K.
Howard, J. Chem. Soc., Dalton Trans. 2001, 292.
[13] S. Szafert, J. A. Gladysz, Chem. Rev. 2003, 103, 4175; S. Szafert,
J. A. Gladysz, Chem. Rev. 2006, 106, PR1.
[14] P. Braunstein, G. Predieri, A. Tiripiccchio, E. Sappa, Inorg. Chim.
Acta 1982, 63, 113.
Acknowledgement
We thank the Australian Research Council for support of this work
and Johnson Matthey plc, Reading, UK, for a generous loan of
RuCl3·nH2O.
[15] W. M. Khairul, D. Albesa-Jové, D. S. Yufit, M. R. Al-Haddad,
J. C. Collings, F. Hartl, J. A. K. Howard, T. B. Marder, P. J. Low,
Inorg. Chim. Acta 2008, 361, 1646.
[16] M. I. Bruce, P. J. Low, K. Costuas, J.-F. Halet, S. P. Best, G. A.
Heath, J. Am. Chem. Soc. 2000, 122, 1949.
[17] M. I. Bruce, M. Jevric, B. W. Skelton, A. H. White, N. N. Zait-
seva, J. Organomet. Chem. 2010, 695, 1906.
References
[18] R. F. Kovar, M. D. Rausch, H. Rosenberg, Organomet. Chem.
Synth. 1971, 1, 173.
[1] a) P. J. Low, M. I. Bruce, Adv. Organomet. Chem. 2001, 48, 71;
b) M. I. Bruce, P. J. Low, Adv. Organomet. Chem. 2004, 50, 179;
c) M. I. Bruce, K. Costuas, T. Davin, J.-F. Halet, K. A. Kramarc-
zuk, P. J. Low, B. K. Nicholson, G. J. Perkins, R. L. Roberts,
B. W. Skelton, M. E. Smith, A. H. White, Dalton Trans. 2007,
5387; d) M. I. Bruce, M. A. Fox, P. J. Low, B. W. Skelton, N. N.
Zaitseva, Dalton Trans. 2010, 39, 3759;
[2] M. I. Bruce, P. J. Low, F. Hartl, P. A. Humphrey, F. de Montigny,
M. Jevric, C. Lapinte, G. J. Perkins, R. L. Roberts, B. W. Skelton,
A. H. White, Organometallics 2005, 24, 5241.
[3] M. I. Bruce, A. G. Swincer, Adv. Organomet. Chem. 1983, 22,
59.
[19] C. Weisemann, G. Schmidtberg, H.-A. Brune, J. Organomet.
Chem. 1989, 365, 403.
[20] M. I. Bruce, G. J. Perkins, B. W. Skelton, A. H. White, Inorg.
Chim. Acta 2006, 359, 2644.
[21] M. I. Bruce, E. Horn, J. G. Matisons, M. R. Snow, Aust. J. Chem.
1984, 37, 1163.
[22] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112.
Received: March 1, 2011
Published Online: May 10, 2011
1212
www.zaac.wiley-vch.de
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 1207–1212