Alkynylphosphanes as supports for mixed-metal Co4M (M = Ru, Os) fluoride complexes: Syntheses, structures and thermolysis studies

Article abstract of DOI:10.1016/j.jorganchem.2007.09.006

Treatment of the tetrameric group eight fluoride complexes [MF(μ-F)(CO)₃]₄ [M = Ru (1a), Os (1b)] with the alkynylphosphane, Ph₂PC{triple bond, long}CPh, results in fluoride-bridge cleavage and the formation of the air-sensitive monomeric octahedral complexes [MF₂(CO)₂(PPh₂CCPh)₂] [M = Ru (2a), Os (2b)] in high yield. The molecular structure of 2b reveals a cis, cis, trans configuration for each pair of ligands, respectively. The free alkyne moieties in 2 can be readily complexed to hexacarbonyldicobalt fragments by treatment with dicobalt octacarbonyl to afford [MF₂(CO)₂(μ-η¹:η²-PPh₂CCPh)₂{Co₂(CO)₆}₂] [M = Ru (3a), Os (3b)]. Evidence for an intramolecular non-bonded contact between a bound fluoride and a cobalt carbonyl carbon atom is seen in the molecular structure of 3a. Thermolysis of 3a at 50 °C results in fluoride dissociation to give [RuF(CO)₂(μ-η¹:η²-PPh₂CCPh)₂{Co₂(CO)₆}₂]⁺ (4), while no reaction occurred with the osmium analogue. Prolonged thermolysis at 120 °C in a sealed vessel of both 3a and 3b gave only insoluble decomposition products.

Full text of DOI:10.1016/j.jorganchem.2007.09.006

Available online at www.sciencedirect.com
Journal of Organometallic Chemistry 692 (2007) 5474–5480
www.elsevier.com/locate/jorganchem
Alkynylphosphanes as supports for mixed-metal Co4M (M = Ru,
Os) fluoride complexes: Syntheses, structures and thermolysis studies
*
Duncan A.J. Harding, Eric G. Hope, John Fawcett, Gregory A. Solan
Department of Chemistry, University of Leicester, University Road, Leicester LE1 7RH, UK
Received 10 August 2007; received in revised form 31 August 2007; accepted 4 September 2007
Available online 12 September 2007
Abstract
Treatment of the tetrameric group eight fluoride complexes [MF(l-F)(CO)3]4 [M = Ru (1a), Os (1b)] with the alkynylphosphane,
Ph2PC„CPh, results in fluoride-bridge cleavage and the formation of the air-sensitive monomeric octahedral complexes
[MF2(CO)2(PPh2CCPh)2] [M = Ru (2a), Os (2b)] in high yield. The molecular structure of 2b reveals a cis, cis, trans configuration for
each pair of ligands, respectively. The free alkyne moieties in 2 can be readily complexed to hexacarbonyldicobalt fragments by treatment
with dicobalt octacarbonyl to afford [MF2(CO)2(l-g1:g2-PPh2CCPh)2{Co2(CO)6}2] [M = Ru (3a), Os (3b)]. Evidence for an intramolec-
ular non-bonded contact between a bound fluoride and a cobalt carbonyl carbon atom is seen in the molecular structure of 3a. Ther-
molysis of 3a at 50 ꢀC results in fluoride dissociation to give [RuF(CO)2(l-g1:g2-PPh2CCPh)2{Co2(CO)6}2]+ (4), while no reaction
occurred with the osmium analogue. Prolonged thermolysis at 120 ꢀC in a sealed vessel of both 3a and 3b gave only insoluble decom-
position products.
ꢁ 2007 Elsevier B.V. All rights reserved.
Keywords: Alkynylphosphanes; Hexacarbonyldicobalt; Ruthenium; Osmium; Fluoride; Thermolysis
1. Introduction
interested in exploring the reactivity of the tetrameric
group 8 fluoride complexes [MF(l-F)(CO)3]4 (M = Ru,
1a; Os, 1b; Fig. 1) towards two electron donors and have
found that with simple monodentate phosphanes scission
of divalent metal complex 1 occurs to give monomeric spe-
cies of the type cis,cis,trans-[MF2(CO)2(PR3)2] [2: M = Ru,
Os; PR3 = PPh3, PEt2Ph, P(C6H11)3] [10]. Notably, as the
steric bulk of the phosphane increases reactivity is inhibited
with only products resulting from decomposition of 1 being
observed [11].
In this paper, we are concerned with exploiting the
bifunctional nature of the alkynylphosphane, Ph2PC„CPh
[12], to prepare more sterically bulky examples of com-
plexes of type 2. Specifically, polymetallic Co4M (Ru, Os)
difluoride species are being targeted with a view to probing
their potential thermolytically initiated fragmentation/cou-
pling chemistry. This program has been further fuelled by
reports of P–F coupling reactions [13] and fluoroacyl for-
mation [10b,14] in related late transition metal fluoride
complexes.
The application of alkynylphosphanes (PR2C„CR,
R = hydrocarbyl) in organometallic chemistry has been
the subject of considerable research activities over the last
three decades which can, in part, be attributed to their poly-
functional nature [1,2] and also to their capacity to undergo
coupling/insertion reactions with other coordinated groups
[3–7]. These coupling reactions can occur with the intact
ligand [3,4] or with units derived from fragmentation of
the alkynylphosphane (e.g., phosphide and acetylide) [5–
7]. In addition, their use to promote the formation of homo-
and hetero-metallic clusters has been documented [8].
Interest in low valent transition metal fluorides contin-
ues to grow, particularly for their roles in coordination
chemistry and fluoroorganic synthesis [9]. We have been
*
Corresponding author. Tel.: +44 (0) 116 252 2096; fax: +44 (0) 116 252
3789.
E-mail address: gas8@leicester.ac.uk (G.A. Solan).
0022-328X/$ - see front matter ꢁ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.09.006

D.A.J. Harding et al. / Journal of Organometallic Chemistry 692 (2007) 5474–5480
5475
2b is shown in Fig. 2; selected bond lengths and angles
are presented in Table 2. The structure consists of a sin-
gle osmium atom bound by two fluorides, two carbonyl
ligands and two alkynylphosphane ligands to complete
a distorted octahedral geometry. The pairs of fluoride
and carbonyl ligands and disposed mutually cis while
the alkynylphosphanes are trans [P(1)–Os(1)–P(2) 173.44-
(5)ꢀ] to one another, a relative disposition also seen in
trans-[Ru(acac)2(Ph2PCCR)2] (R = H, Me, Ph) [16]. Each
alkynic unit points in a similar direction to a carbonyl
ligand which is likely stabilised through hydrogen bond-
ing interactions involving an ortho-hydrogen atom on
one alkynic phenyl group and a carbonyl oxygen atom
CO
M
OC
F
CO
F
CO
M
CO
CO
F
F
OC
F
CO
F
M
F
CO
CO
CO
M
F
CO
1a M = Ru
1b
M = Os
˚
˚
[O(2)ꢀ ꢀ ꢀH(30) 3.105 A, O(1)ꢀ ꢀ ꢀH(6) 2.713 A]. The C–O
and Os–F bond lengths are similar those reported for
the structurally related complex cis,cis,trans-[OsF2(CO)2-
(PPh3)2] [10a]. No significant intermolecular interactions
are apparent.
Fig. 1. Tetrameric [MF(l-F)(CO)3] (1).
2. Results and discussion
Interaction of [MF(l-F)(CO)3]4 [M = Ru (1a), Os (1b)]
[15] with eight equivalents of Ph2PC„CPh in tetrahydro-
furan at ambient temperature afforded cis,cis,trans-
[MF2(CO)2(Ph2PCCPh)2] [M = Ru (2a), Os (2b)] in good
yield (Scheme 1). Both complexes have been characterised
Two m(CO) bands are seen in the IR spectra for both 2a
and 2b, the stretching frequencies in osmium 2b being ca.
20 cmꢁ1 less than those for ruthenium 2a and resembling
the trend seen for the structurally related complexes
[MX2(CO)2(PPh3)2] (M = Ru, Os; X = Cl, Br, I) [10a]. In
the mass spectra of 2a and 2b, fragmentation peaks are evi-
dent corresponding to the loss of fluoride and carbonyl
ligands from their molecular ions. Their 19F NMR spectra
reveal resonances at d ꢁ336.7 (2a) and d ꢁ315.6 (2b) for
the fluoride ligands that take the form of triplets with the
phosphorus–fluorine coupling constants [24 Hz (2a),
33 Hz (2b)] comparable to those seen in [MF2(CO)2(PPh3)2]
[20 Hz (Ru), 30 Hz (Os)] [10a].
1
by IR, H, 19F and 31P NMR spectroscopy and gave satis-
factory microanalyses (see Table 1 and Section 4). In addi-
tion, 2b has been the subject of a single crystal X-ray
diffraction study.
Crystals of 2b suitable for the X-ray determination
were grown by slow vapour diffusion of hexane into a
saturated dichloromethane solution containing the com-
plex at room temperature. The molecular structure of
Ph2P
M
Ph
Ph
(i)
(ii)
OC
OC
F
F
1
M3(CO)12
M = Ru, Os
Ph2P
2a M = Ru
2b M = Os
(iii)
(OC)6Co2
Ph
Ph
Ph2P
OC
(OC)6Co2
Ph2P
(M = Ru)
Ru
F
Ph
Ph
OC
Ph2P
OC
(iv)
F
M
(OC)6Co2
OC
F
4
Ph2P
(OC)6Co2
3a M = Ru
(M = Os)
no reaction
3b M = Os
Scheme 1. Reagents and conditions: (i) F2, anhydrous HF [15]; (ii) Ph2PCCPh, THF, 12 h; (iii) Co2(CO)8, CH2Cl2, 24 h; (iv) 50 ꢀC, CDCl3, 20 h.

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D.A.J. Harding et al. / Journal of Organometallic Chemistry 692 (2007) 5474–5480
Table 1
Spectroscopic and analytical data for the new complexes
Complex m(CO) (cmꢁ1 a
)
1H NMR (d)b
19F NMR (d)c
31P NMR (d)d
Microanalysis (%)e
C
H
2
2
2a
2b
3a
2039(s), 1966(s)
8.20–8.12 (m, 20H, Ar-H),
7.55–7.30 (m, 10H, Ar-H)
8.10, 7.60–7.30 (m, 30H,
Ar-H)
8.15, 7.80, 7.40–7.20
(m, 30H, Ar-H)
ꢁ336.7 (t, JPF 24, Ru–F) ꢁ5.5 (t, JPF 24, Ru–P)
65.60 (65.71) 3.85 (3.91)
59.04 (58.74) 3.39 (3.50)
48.36 (48.39) 2.20 (2.24)
2
2
2020(s), 1937(s)
ꢁ315.6 (t, JPF 33, Os–F)
ꢁ23.1 (t, JPF 33, Os–P)
2
2
2092(s), 2072(s),
2062(s), 2030(br),
2018(br), 1995(br),
1958(br)
2093(s), 2071(br),
2062(br), 2036(br),
2014(br), 1996(br),
1936(br)
ꢁ306.2 (t, JPF 26, Ru–F) 29.0 (t, JPF 26, Ru–P)
2
2
3b
7.90–7.00 (m, 30H, Ar-H)
ꢁ285.3 (t, JPF 34, Os–F)
10.6 (t, JPF 34, Os–P)
45.25 (45.19) 1.90 (1.94)
a
b
c
Recorded on a Perkin–Elmer Spectrum One FT-IR spectrometer on solid samples.
Recorded in CDCl3 at 293 K, chemical shifts in ppm relative to SiMe4 (0.0 ppm).
Recorded in CDCl3 at 293 K, chemical shifts in ppm relative to CFCl3 (0.0 ppm), coupling constants in Hz.
Recorded in CDCl3 at 293 K, chemical shifts in ppm relative to 85% H3PO4 (0.0 ppm), coupling constants in Hz.
Calculated values shown in parentheses.
d
e
Table 2
˚
Selected bond distances (A) and angles (ꢀ) for 2b
˚
Bond lengths (A)
Os(1)–F(1)
Os(2)–F(2)
Os(1)–C(1)
Os(1)–C(2)
Os(1)–P(1)
Os(1)–P(2)
P(1)–C(17)
2.023(3)
2.023(3)
1.872(5)
1.868(5)
2.3795(13)
2.3797(14)
1.816(5)
P(1)–C(11)
P(1)–C(3)
1.826(5)
1.746(5)
1.211(7)
1.797(5)
1.818(5)
1.756(5)
1.188(7)
C(3)–C(4)
P(2)–C(31)
P(2)–C(37)
P(2)–C(23)
C(23)–C(24)
Bond angles (ꢀ)
F(1)–Os(1)–F(2)
F(1)–Os(1)–C(1)
F(1)–Os(1)–C(2)
F(1)–Os(1)–P(1)
F(1)–Os(1)–P(2)
F(2)–Os(1)–C(1)
F(2)–Os(1)–C(2)
83.47(11)
92.53(18)
177.11(18)
89.62(9)
86.15(9)
93.95(17)
93.95(17)
F(2)–Os(1)–P(1)
F(2)–Os(1)–P(2)
P(1)–Os(1)–P(2)
Os(1)–P(1)–C(3)
P(1)–C(3)–C(4)
Os(1)–P(2)–C(23)
P(2)–C(23)–C(24)
86.53(9)
88.00(9)
173.44(5)
111.07(18)
170.7(5)
111.61(18)
169.4(5)
ane mixture containing the complex. The complex crystal-
lises with two discrete independent molecules (A and B in
Table 3) within its asymmetric unit. The molecular struc-
ture of 3a (molecule A) is shown in Fig. 3; selected bond
distances and angles for bond A and B are listed in Table
3. The main difference between the two molecules derives
from the relative inclination of the phenyl groups. The
molecular structure of 3a consists of a single octahedral
ruthenium centre bound by two cis-fluorides, two cis-car-
bonyls and two trans-phosphanes in a manner similar to
that seen for 2b and [RuF2(CO)2(PPh2Et)2] [10a]. Unlike
in 2b, however, the alkynic moieties within the phosphanes
are additionally bound by g2:g2-Co2(CO)6 units; the geo-
metric parameters of the pseudo-tetrahedral Co2C2 cores
are unexceptional. In comparison to [RuF2(CO)2(P-
Ph2Et)2] [10a], it is apparent that the presence of coordi-
nated Co2(CO)6 units in 3a has little effect on the Ru–F,
Ru–P and Ru–C bond distances. As with 2b one ortho-
hydrogen atom per alkynyl phenyl group undergoes a
Fig. 2. Molecular structure of 2b with partial atom labeling scheme; all
hydrogen atoms have been omitted for clarity.
With the intent of increasing the steric properties of the
two P-coordinated alkynylphosphanes in 2, the reactivity
of the free alkynic units towards dicobalt octacarbonyl
was examined. Hence, interaction of 2 with two equivalents
of [Co2(CO)8] at room temperature gave, on work-up,
[MF2(CO)2(l-g1:g2-PPh2CCPh)2{Co2(CO)6}2] [M = Ru
(3a), Os (3b)] in high yield (Scheme 1). Both complexes
have been characterised by IR, 1H, 19F and 31P NMR spec-
troscopy and gave satisfactory microanalyses (see Table 1
and Section 4). In addition, 3a has been the subject of a sin-
gle crystal X-ray diffraction study.
Crystals of 3a suitable for the X-ray determination were
grown by prolonged standing of a hexane–dichlorometh-

D.A.J. Harding et al. / Journal of Organometallic Chemistry 692 (2007) 5474–5480
5477
Fig. 3. Molecular structure of 3a with partial atom labeling scheme; all hydrogen atoms have been omitted for clarity.
Table 3
hydrogen bonding interaction, in this case, however, with a
˚
Selected bond distances (A) and angles (ꢀ) for 3a
˚
˚
fluoride [C(24)Hꢀ ꢀ ꢀF(2) 2.142 A, C(38)Hꢀ ꢀ ꢀF(1) 2.150 A]
rather than with a carbonyl oxygen atom. In addition, an
intramolecular non-bonded contact is evident between
Molecule A
Molecule B
˚
Bond lengths (A)
Ru(1)–F(1)
Ru(2)–F(2)
Ru(1)–C(1)
Ru(1)–C(2)
Ru(1)–P(1)
Ru(1)–P(2)
P(1)–C(25)
2.017(6)
1.989(6)
1.843(12)
1.833(12)
2.392(3)
2.417(3)
1.805(10)
1.821(10)
2.017(6)
1.993(6)
1.814(12)
1.840(10)
2.404(3)
2.398(3)
1.793(11)
1.822(10)
˚
F(2) and cobalt carbonyl C(8) [2.664 A]. This type of
Fꢀ ꢀ ꢀCCO interaction is not unprecedented, but is usually
only observed intermolecularly between ‘superelectrophilic’
metal carbonyl cations and fluoro-anions of either anti-
mony or boron [17]. No significant intermolecular interac-
tions are apparent.
P(1)–C(31)
The spectroscopic data for 3 are consistent with the solid
state properties being maintained in solution. In the 19F
NMR spectra, triplets are seen for the equivalent fluoride
ligands in 3a and 3b with chemical shifts and phosphorus-
fluorine coupling constants similar to those seen for 2a
and 2b, respectively. The IR spectra show a series of m(CO)
bands in a pattern characteristic of other Co2(CO)6-alkyne
complexes [18] along with lower wavenumber m(CO) bands
that can be attributed to the group eight metal carbonyl
groups. The 31P NMR spectra of 3a and 3b reveal triplet res-
onances for the equivalent phosphorus atoms shifted ca.
30 ppm downfield with regard to 2a and 2b, consistent with
the loss of the alkyne p-system on coordination [8c,19].
In order to probe the capacity of 3 to undergo fragmen-
tation reactions (e.g., P–C bond cleavage, fluoride migra-
tion), a spectroscopic study on the thermolysis of 3a and
3b was undertaken. Separate NMR tubes were charged
with solutions of 3 in CDCl3 and sealed. Osmium complex
3b remained unaffected by heating in CDCl3 at 50 ꢀC, with
no decomposition or formation of any other species being
apparent. Prolonged heating of 3b in toluene-d8 at 120 ꢀC
resulted in the formation of intractable decomposition
products.
P(2)–C(49)
P(2)–C(43)
1.823(11)
1.806(10)
1.764(15)–1.819(15)
1.114(13)–1.206(11)
1.949(9)–1.993(11)
1.470(15)
1.476(13)
2.4552(19)
2.454(2)
1.806(10)
1.803(10)
1.784(16)–1.849(14)
1.112(12)–1.185(12)
1.946(12)–1.962(10)
1.515(14)
1.483(15)
2.461(2)
2.4519(19)
Co–C(carbonyl)
C–O(carbonyl)
Co–C(alkyne)
C(18)–C(37)
C(16)–C(19)
Co(1)–Co(2)
Co(3)–Co(4)
Bond angles (ꢀ)
F(1)–Ru(1)–F(2)
F(1)–Ru(1)–C(1)
F(1)–Ru(1)–C(2)
F(1)–Ru(1)–P(1)
F(1)–Ru(1)–P(2)
F(2)–Ru(1)–C(1)
F(2)–Ru(1)–C(2)
F(2)–Ru(1)–P(1)
F(2)–Ru(1)–P(2)
P(1)–Ru(1)–P(2)
Ru(1)–P(1)–C(15)
P(1)–C(15)–C(16)
C(19)–C(16)–C(15)
Ru(1)–P(2)–C(17)
P(2)–C(17)–C(18)
C(17)–C(18)–C(37)
86.0(2)
92.9(4)
85.6(2)
94.4(4)
175.6(4)
87.79(18)
86.56(18)
176.4(4)
89.8(4)
86.03(18)
87.18(18)
171.44(10)
113.7(3)
143.0(8)
142.8(9)
115.3(4)
146.1(9)
144.2(11)
174.3(3)
86.02(18)
88.67(18)
178.4(3)
89.0(4)
86.30(17)
86.30(17)
171.55(10)
117.1(4)
146.6(9)
141.4(11)
113.1(3)
145.4(8)
140.6(9)

5478
D.A.J. Harding et al. / Journal of Organometallic Chemistry 692 (2007) 5474–5480
However, after heating a CDCl3 solution of ruthenium
4. Experimental
complex 3a at 50 ꢀC for 4 h, both the 31P and 19F NMR
data supported the formation of a new complex. In the
31P NMR spectrum, a signal corresponding to the starting
material was flanked by a new doublet at d 26.6, while in
the 19F NMR spectrum the additional fluorine signal took
the form of a mutually coupled triplet (2JPF 27 Hz) at d
ꢁ348.4. After heating at 50 ꢀC for a further 16 h the
transformation was complete. In the resultant 19F NMR
spectrum, the mutually coupled triplet at d ꢁ348.4 was
accompanied by two small singlets at d ꢁ113.1 and d
ꢁ139.6. The spectroscopic data indicate that thermolysis
of 3a causes the formation of a single fluorine- and phos-
phane-containing cation [RuF(CO)2(l-g1:g2-PPh2CCPh)2-
{Co2(CO)6}2]+ (4) (Scheme 1). The triplet in the 19F NMR
spectrum of 4 is substantially upfield shifted when com-
pared to that for the parent complex 3a and falls in the
range found for previously reported related mono-fluoro
ruthenium cationic complexes [20]. The singlets at d
ꢁ113.1 and d ꢁ139.6 observed in the 19F NMR spectrum
during the transformation of 3a to 4 are most likely due
to varying degrees of solvent fluorination [21], suggesting
that thermolysis of 3a (and formation of 4) involves fluo-
ride dissociation from the metal. It is uncertain as to the
precise nature of the anion in 4 but a chloride ion (or a
Cl-containing species), generated during fluorination of
the chlorinated NMR solvent, would seem likely. Heating
a toluene-d8 solution of 3a to 120 ꢀC resulted in the forma-
tion of intractable decomposition products.
4.1. General procedures and materials
All reactions, unless otherwise stated, were carried out
under an atmosphere of dry, oxygen-free nitrogen, using
standard Schlenk techniques or in a nitrogen purged dry
box. Solvents were distilled under nitrogen from appropri-
ate drying agents and degassed prior to use [22]. The infra-
red spectra were recorded on a Perkin–Elmer Spectrum
One FT-IR spectrometer on solid samples. The ES (electro-
spray) and the FAB mass spectra were recorded using a
micromass Quattra LC mass spectrometer and a Kratos
Concept spectrometer with methanol or 3-nitrobenzyl alco-
1
hol as the matrix, respectively. H, 31P, 19F and 13C NMR
spectra were recorded on a Bruker spectrometer (ARX 250,
AM 300 or DRX 400 MHz) at ambient temperature; chem-
1
ical shifts (d) for the H and 13C NMR spectra were refer-
enced internally to TMS (d = 0) while 19F and 31P were
referenced externally to CFCl3 (d = 0) and 85% H3PO4
(d = 0), respectively. Elemental analyses were performed
at the Science Technical Support Unit, London Metropol-
itan University.
The compounds, (tricarbonyl)rutheniumdifluoride tetra-
mer (1a) [15], (tricarbonyl)osmiumdifluoride tetramer (1b)
[15] and phenylethynyldiphenylphosphane [12], were pre-
pared according to previously reported procedures while
dicobalt octacarbonyl was obtained from Aldrich Chemical
Co. and used without further purification. All other chem-
icals were obtained commercially and used without further
purification.
Unfortunately, attempts to fill the vacant coordination
site in 4 with CO or acetonitrile failed with the correspond-
ing NMR spectra revealing only the presence of unreacted
starting material. This may be rooted in steric protection of
the metal centre in 4, or intramolecular stabilisation inter-
actions between the ruthenium centre and the pendant car-
bonyl groups of the (l-g1:g2-PPh2CCPh)2{Co2(CO)6}2
fragments. Unfortunately, all attempts to isolate 4 were
unsuccessful, and it was characterised solely by NMR
spectroscopy.
4.2. Synthesis of [MF2(CO)2(PPh2CCPh)2] (2)
4.2.1. (i) M = Ru (2a)
Under an atmosphere of nitrogen a Schlenk vessel was
charged with 1a (0.250 g, 0.280 mmol) and Ph2PCCPh
(0.657 g, 2.296 mmol) and freshly distilled tetrahydrofuran
(40 mL) introduced. After stirring the reaction mixture at
room temperature for 12 h under a partial vacuum, the
volatiles were removed under reduced pressure and the
residue washed with methanol (2 · 5 mL). Recrystalliza-
tion from a mixture of tetrahydrofuran and hexane gave
[RuF2(CO)2(PPh2CCPh)2] (2a) as an air- and moisture-
sensitive white powder. Yield: 0.515 g, 60%. IR (cmꢁ1):
3048 w, 2163 (C„C), 2039s (CO), 1966s (CO), 1480m,
1435s, 1094m, 848s, 683s. 13C {1H} NMR (CDCl3): d
195.3 (CO), 132.9, 131.1 (Ar-CH), 129.9 (Ar-C), 128.6
(Ar-CH), 112.3 (P–C„C), 79.4 (PC„C). FAB mass spec-
trum, m/z 721 [MHꢁFꢁCO]+, 701 [Mꢁ2FꢁCO]+, 673
[Mꢁ2Fꢁ2CO]+.
3. Conclusions
In this study, we have shown that Ph2PC„CPh can be
readily introduced into the coordination sphere of a group
8 (M = Ru, Os) fluoride complex as a P-donor ligand to
afford octahedral 2. Complexation of the alkynic moieties
within 2 with dicobalt hexacarbonyl groups preserves the
MF2 core by generating the mixed-metal Co4M (M = Ru,
Os) clusters 3. Thermolysis of 3a at 50 ꢀC leads to the for-
mation of another complex, which was spectroscopically
characterised as [RuF(CO)2(l-g1:g2-PPh2CCPh)2{Co2-
(CO)6}2]+ (4), formed by dissociation of one of the fluoride
ligands. Under similar conditions, no reaction of 3b was
observed, indicating an increased stability of the Os–F bond
in 3b when compared to the Ru–F bond of 3a. Exposing
either 3a or 3b to more forcing conditions led to the forma-
tion of intractable decomposition products.
4.2.2. (ii) M = Os (2b)
Using a similar procedure, 1b (0.349 g, 0.280 mmol) and
Ph2PCCPh (0.657 g, 2.296 mmol) gave [OsF2(CO)2-
(PPh2CCPh)2] (2b) as an air- and moisture-sensitive white

D.A.J. Harding et al. / Journal of Organometallic Chemistry 692 (2007) 5474–5480
5479
2
powder. Yield: 0.594 g, 62%. Crystals suitable for X-ray
diffraction were grown by slow vapour diffusion of hexane
into a saturated dichloromethane solution of 2b. IR
(cmꢁ1): 3048w, 2162 (C„C), 2020s (CO), 1937s (CO),
1484s, 1434s, 850s, 688s. FAB mass spectrum, m/z 839
[MꢁF]+, 811 [MꢁFꢁCO]+, 783 [MꢁFꢁ2CO]+, 764
[Mꢁ2Fꢁ2CO]+.
26.6 (d, JPF 27, Ru–P). Heating a solution of 3a in tolu-
ene-d8 at 120 ꢀC resulted in the formation of intractable
decomposition products.
4.4.2. (ii) M = Os (3b)
Using a similar protocol, 3b (0.050 g, 0.035 mmol) and
CDCl3 (1 mL). After heating at 50 ꢀC, 3b could be recov-
ered intact. Prolonged heating of 3b in toluene-d8 at
120 ꢀC resulted in the formation of intractable decomposi-
tion products.
4.3. Synthesis of [MF2(CO)2(l-g1:g2-PPh2CCPh)2-
{Co2(CO)6}2] (3)
4.3.1. (i) M = Ru (3a)
4.5. Crystallographic studies
Under an atmosphere of nitrogen a Schlenk tube was
charged with 2a (0.400 g, 0.522 mmol) and dicobaltoctacar-
bonyl (0.357 g, 1.043 mmol) and freshly distilled dichloro-
methane (10 mL) introduced. After stirring the red
solution at room temperature for 24 h the volatiles were
removed under reduced pressure to give a dark red solid.
Recrystallisation of the solid from a mixture of dichloro-
methane and hexane gave 3a as air- and moisture-sensitive
deep red needles. Yield: 0.559 g, 80%. Crystals suitable for
an X-ray diffraction study were grown by vapour diffusion
of hexane into a saturated dichloromethane solution. IR
(cmꢁ1): 3053w, 2092 (CO), 2072s (CO), 2062s (CO),
2030br (CO), 2018br (CO), 1995br (CO), 1958br (CO),
1480s, 1432s, 1094s, 695s. 13C {1H} NMR (CDCl3): d
198.3 (CO), 138.2 (Ar-C), 134.0 (Ar-C), 133.9 (Ar-CH),
131.5 (Ar-CH), 130.9 (Ar-CH), 128.5 (Ar-CH), 128.1 (Ar-
CH), 105.8 (P–C„C), 77.1 (PC„C). FAB mass spectrum,
m/z 1227 [Mꢁ4CO]+, 1199 [Mꢁ5CO]+, 1115 [Mꢁ8CO]+,
1087 [Mꢁ9CO]+, 1059 [Mꢁ10CO]+.
Data for 2b and 3a were collected on a Bruker APEX
2000 CCD diffractometer. Details of data collection, refine-
ment and crystal data are listed in Table 4. The data were
corrected for Lorentz and polarisation effects and empirical
absorption corrections applied. Structure solution by direct
methods and structure refinement based on full-matrix
least-squares on F2 employed SHELXTL version 6.10 [23].
Hydrogen atoms were included in calculated positions
˚
(C–H = 0.96 A) riding on the bonded atom with isotropic
displacement parameters set to 1.5Ueq(C) for methyl H
atoms and 1.2Ueq(C) for all other H atoms. All non-H
atoms were refined with anisotropic displacement
parameters.
Table 4
Crystallographic and data processing parameters for 2b and 3a
Complex
2b
3a
Formula
C
42H30F2O2OsP2
C54H30Co4F2O14P2Ru
1339.51
0.47 · 0.10 · 0.03
150
Molecular weight
Crystal size (mm3)
Temperature (K)
Crystal system
Space group
856.80
0.34 · 0.07 · 0.06
150
trigonal
P31
10.7451(13)
10.7451(13)
26.256(5)
90
90
120
2625.3(7)
3
1.626
4.3.2. (ii) M = Os (3b)
Using a similar procedure, 2b (0.477 g, 0.522 mmol) and
dicobaltoctacarbonyl (0.357 g, 1.043 mmol) gave [OsF2-
(CO)2(l-g1:g2-PPh2CCPh)2{Co2(CO)6}2] (3b) as an air-
and moisture-sensitive deep red powder. Yield: 0.447 g,
60%. IR (cmꢁ1): 3294br, 2093 (CO), 2071br (CO), 2062br
(CO), 2036br (CO), 2014br (CO), 1996br (CO), 1936br
(CO), 1561s, 1432s, 1094s, 688s. FAB mass spectrum,
m/z 1289 [Mꢁ5CO]+, 1205 [Mꢁ8CO]+, 1117 [Mꢁ9CO]+,
1149 [Mꢁ10CO]+, 1121 [Mꢁ11CO]+, 1093 [Mꢁ12CO]+,
1065 [Mꢁ14CO]+, 975 [Mꢁ14COꢁ2Co]+.
triclinic
ꢀ
P1
˚
a (A)
9.6526(11)
19.844(2)
28.972(3)
104.777(2)
91.295(2)
90.072(2)
5364.5(11)
4
˚
b (A)
˚
c (A)
a (ꢀ)
b (ꢀ)
c (ꢀ)
3
˚
V (A )
Z
Dcalc (Mg mꢁ3
F(000)
)
1.659
2664
1.618
1266
3.781
l(Mo Ka) (mmꢁ1
)
4.4. Thermolysis of [MF2(CO)2(l-g1:g2-PPh2CCPh)2-
{Co2(CO)6}2] (3)
Reflections collected
Independent reflections
Rint
22132
7546
0.0549
1/442
38792
18721
0.0814
0/1387
Restraints/parameters
4.4.1. (i) M = Ru (3a)
Final R indices [I > 2r(I)] R1 = 0.0298,
wR2 = 0.0604
Final R indices (all data) R1 = 0.0315,
wR2 = 0.0609
Goodness of fit on F2 (all 1.024
data)
R1 = 0.0842,
wR2 = 0.1899
R1 = 0.1392,
wR2 = 0.2181
0.928
Complex 3a (0.050 g, 0.037 mmol) was dissolved in
CDCl3 (1 mL) in an NMR tube under a nitrogen atmo-
sphere. The tube was sealed, and immersed in an oil bath
which was held at 50 ꢀC. After 20 h, the 19F and 31P
NMR spectra revealed complete reaction of 3a, with con-
comitant formation of [RuF(CO)2(l-g1:g2-PPh2CCPh)2-
{Co2(CO)6}2]+ (4). 1H NMR (CDCl3): d 8.10, 7.75,
7.45–7.20 (m, 30H, Ar-H); 19F {1H} NMR (CDCl3): d
Data in common: graphite-monochromated Mo Ka radiation, k =
P
P
P
P
0.71073 A; R1 = iFoj ꢁ jFci/ jFoj, wR2 = [ w(Fo ꢁ Fc2)2/ w(Fo2)2]1/2
,
2
˚
w
ꢁ1 = [r2(Fo)2 + (aP)2], P = [max(Fo2,0) + 2(Fc2)]/3, where a is a constant
P
adjusted by the program; goodness of fit = [ (Fo ꢁ Fc2)2/(n ꢁ p)]1/2
2
2
ꢁ348.4 (t, JPF 27, Ru–F); 31P {1H} NMR (CDCl3): d
where n is the number of reflections and p the number of parameters.

5480
D.A.J. Harding et al. / Journal of Organometallic Chemistry 692 (2007) 5474–5480
[7] (a) I. Ara, J. Fornies, A. Garcia, J. Gomez, E. Lalinde, M.T.
Acknowledgement
Moreno, Chem.-Eur. J. 8 (2002) 3698;
(b) I. Ara, L.R. Falvello, S. Fernandez, J. Fornies, E. Lalinde, A.
Martin, M.T. Moreno, Organometallics 16 (1997) 5923;
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(1979) 5422;
We acknowledge the EPSRC for financial support.
Appendix A. Supplementary data
(d) D.K. Johnson, T. Rukachaisinku, Y. Sun, N.J. Taylor, A.J.
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CCDC 656947 and 656946 contain the supplementary
crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallo-
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