Phosphorus-hydrogen bond cleavage on a Ph2PH-substituted μ3-thioxo dicobalt-iron cluster as a route to bridging phosphido and thiophosphine ligands

Article abstract of DOI:10.1016/S0022-328X(01)01227-X

The secondary phosphine-substituted (at cobalt) mixed-metal dicobalt-iron complex [Co₂Fe(μ₃-S)(CO)₈(PPh₂H)] (1) can be prepared in good yield from the reaction of [Co₂Fe(μ₃-S)(CO)₉] with one equivalent of Ph₂PH in toluene. Also isolated in the reaction, as minor products, are the disubstituted (both at cobalt) complex [Co₂Fe(μ₃-S)(CO)₇(PPh₂H)₂] (2) and the trisubstituted species [Co₂Fe(μ₃-S)(CO)₆(PPh₂H)₃] (3). Thermolysis of 1 or 2 results in PH bond cleavage and the formation of the bis-phosphido-bridged species [Co₂Fe(μ₃-S)(μ-PPh₂)₂(CO)₆] (4) and [Co₂Fe(μ₃-S)(μ-PPh₂)₂(CO)₅(PPh₂H)] (5). Complex 5 can also be prepared more directly by treatment of 4 with one equivalent of Ph₂PH. The X-ray structure of the PhPMe₂ analogue of 5, [Co₂Fe(μ₃-S)(μ-PPh₂)₂(CO)₅(PPhMe₂)] (5′), reveals the phosphine to be cobalt-bound and occupying an equatorial site. Carbonylation of 4 results in coupling of one phosphido group with the sulphur cap to give the thiophosphine-bridged complex [Co₂Fe(μ₃-SPPh₂)(μ-PPh₂)(CO)₇] (6), while treatment of 1 with n-BuLi followed by RSCH₂Cl (R=Me, Ph) results in the formation of the previously reported thiophosphinomethane-bridged species [Co₂Fe(μ₃-S)(μ-PPh₂CH₂SR)(CO)₈] (R=Me 7a, Ph 7b). In contrast, interaction of 1 with n-BuLi followed by successive treatment with carbon disulphide and methyl iodide yields the dithiomethoxycarbonylphosphine-bridged complex [Co₂Fe(μ₃-S){μ-PPh₂C(SMe)S}(CO)₈] (8). Single crystal X-ray diffraction studies have been performed on complexes 5′ and 8.

Full text of DOI:10.1016/S0022-328X(01)01227-X

Journal of Organometallic Chemistry 642 (2002) 227–236
www.elsevier.com/locate/jorganchem
Phosphorus–hydrogen bond cleavage on a Ph2PH-substituted
m3-thioxo dicobalt–iron cluster as a route to bridging phosphido
and thiophosphine ligands
Jason D. King a, Martin J. Mays a,*, Chi-Yu Mo a, Gregory A. Solan b,
Gra´inne Conole c, Mary McPartlin c
a Uni6ersity Chemical Laboratory, Department of Chemistry, Lensfield Road, Cambridge CB2 1EW, UK
b Department of Chemistry, Uni6ersity of Leicester, Uni6ersity Road, Leicester LE1 7RH, UK
c School of Applied Chemistry, Uni6ersity of North London, Holloway Road, London N7 8DB, UK
Received 2 August 2001; accepted 21 August 2001
Abstract
The secondary phosphine-substituted (at cobalt) mixed-metal dicobalt–iron complex [Co2Fe(m3-S)(CO)8(PPh2H)] (1) can be
prepared in good yield from the reaction of [Co2Fe(m3-S)(CO)9] with one equivalent of Ph2PH in toluene. Also isolated in the
reaction, as minor products, are the disubstituted (both at cobalt) complex [Co2Fe(m3-S)(CO)7(PPh2H)2] (2) and the trisubstituted
species [Co2Fe(m3-S)(CO)6(PPh2H)3] (3). Thermolysis of 1 or 2 results in PꢀH bond cleavage and the formation of the
bis-phosphido-bridged species [Co2Fe(m3-S)(m-PPh2)2(CO)6] (4) and [Co2Fe(m3-S)(m-PPh2)2(CO)5(PPh2H)] (5). Complex 5 can also
be prepared more directly by treatment of 4 with one equivalent of Ph2PH. The X-ray structure of the PhPMe2 analogue of 5,
[Co2Fe(m3-S)(m-PPh2)2(CO)5(PPhMe2)] (5%), reveals the phosphine to be cobalt-bound and occupying an equatorial site. Carbony-
lation of 4 results in coupling of one phosphido group with the sulphur cap to give the thiophosphine-bridged complex
[Co2Fe(m3-SPPh2)(m-PPh2)(CO)7] (6), while treatment of 1 with n-BuLi followed by RSCH2Cl (R=Me, Ph) results in the
formation of the previously reported thiophosphinomethane-bridged species [Co2Fe(m3-S)(m-PPh2CH2SR)(CO)8] (R=Me 7a, Ph
7b). In contrast, interaction of 1 with n-BuLi followed by successive treatment with carbon disulphide and methyl iodide yields
the dithiomethoxycarbonylphosphine-bridged complex [Co2Fe(m3-S){m-PPh2C(SMe)ꢁS}(CO)8] (8). Single crystal X-ray diffraction
studies have been performed on complexes 5% and 8. © 2002 Elsevier Science B.V. All rights reserved.
Keywords: Cobalt; Iron; Phosphido; Thiophosphine; Thiophosphinomethane; Dithioalkoxycarbonylphosphine; Cluster
phosphine followed by reaction of the resulting anion
with a wide variety of electrophiles can be employed to
1. Introduction
furnish novel phosphine ligands, some of which are not
obtainable by alternative routes [3–5].
Recently, we have been interested in multidentate
The scission of a PꢀH bond of a secondary phos-
phine within the co-ordination sphere of a transition
metal complex either thermolytically, photolytically or
unsymmetrical ligands containing phosphorus and sul-
with a strong base has been the subject of numerous
phur donor atoms and have prepared bimetallic transi-
reports [1–5]. Thermolysis or photolysis can lead via
tion metal carbonyl complexes incorporating neutral
oxidative addition to the formation of phosphide and
and monoanionic ligands of the type, Ph2P(SR) [6],
hydride groups which, in the presence of more than one
Ph2PCH2SR [7], [Ph2PS]− [8], [Ph2PCHꢁCRS]− [9] and
metal centre, can form complexes in which these ligands
[Ph2PCHꢁCRCPhCꢁS]− [8] (R=hydrocarbyl). Two
act as bridges [1,2]. Conversely, deprotonation of the
synthetic approaches have, in general, been employed,
namely reaction of the metal carbonyl complex with the
pre-prepared ligand or generation of the ligand in situ
on the bimetallic backbone.
* Corresponding author.
E-mail address: mjm14@cam.ac.uk (M.J. Mays).
0022-328X/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01227-X

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J.D. King et al. / Journal of Organometallic Chemistry 642 (2002) 227–236
Herein we report our findings on the synthesis and
characterisation of the secondary phosphine substituted
dicobalt–iron cluster [Co2Fe(m3-S)(CO)8(PPh2H)]
along with the results of our experiments on the ther-
molysis of 1, and on its deprotonation and subsequent
reaction with sulphur-containing electrophiles. Addi-
tionally, we report the reactions of [Co2Fe(m3-S)(m-
PPh2)2(CO)6] 4 with CO and organophosphines.
For 1, the IR spectrum is similar to those reported
for other monosubstituted phosphine derivatives of
[Co2Fe(m3-S)(CO)9] [10], and the 1H-NMR spectrum
confirms the presence of an intact Ph2PH ligand, show-
ing the phenyl protons and a characteristic doublet
[with 1JPH=361 Hz] for the PꢀH proton in a 10:1
integral ratio. A single broad resonance is seen in the
31P{1H}-NMR spectrum at l 15.4 indicative of co-ordi-
nation to cobalt (59Co has a large quadrupolar mo-
ment). The 13C{1H}-NMR spectrum at 293 K shows
that 1 is highly fluxional, with the carbonyls appearing
as a single resonance at l 202.5 at this temperature.
This observation is consistent with the results obtained
previously for the complex [Co2Fe(m3-S)(CO)8(PBun3)] in
which a four-stage carbonyl exchange process has been
identified [10].
1
2. Results and discussion
2.1. Reaction of [Co2Fe(v3-S)(CO)9] with Ph2PH
The reaction of [Co2Fe(m3-S)(CO)9] with one equiva-
lent of Ph2PH in toluene at 313 K gives the monosub-
stituted complex [Co2Fe(m3-S)(CO)8(PPh2H)] 1 in 62%
yield, the disubstituted derivative [Co2Fe(m3-S)(CO)7-
(PPh2H)2] 2 in 8% yield and the trisubstituted derivative
[Co2Fe(m3-S)(CO)6(PPh2H)3] 3 (Scheme 1) in 4% yield.
Complexes 1–3 have been characterised by mass spec-
trometry, microanalysis and by 1H-, 31P-, 13C-NMR
and IR spectroscopy (see Table 1 and Section 3).
The spectroscopic properties of 1–3 in solution are
consistent with those found by Aime et al. in their
studies of the products of carbonyl substitution by
tertiary phosphines in [Co2Fe(m3-S)(CO)9] [10]. The
spectroscopic data suggest that the Ph2PH ligands in
1–3 occupy equatorial sites on one Co, two Co’s, and
two Co’s and one Fe, respectively. Furthermore, a
Mo¨ssbauer study of [Co2Fe(m3-S)(CO)8(PPh3)] [11] indi-
cates monosubstitution to occur at cobalt at an equato-
rial site and this is supported by the X-ray structure of
the related triphenylphosphite complex [Co2Fe(m3-
S)(CO)8{P(OPh)3}] [12].
Complex 2 again shows properties similar to those
found for other disubstituted phosphine derivatives of
1
[Co2Fe(m3-S)(CO)9] [10]. As with 1, the H-NMR spec-
trum shows a doublet [1JPH=356 Hz] and a multiplet
for the co-ordinated secondary phosphine PꢀH and
phenyl proton resonances, respectively, and the single
broad 31P{1H}-NMR peak [l 15.3] indicates that the
two P atoms are equivalent and located on two differ-
ent cobalt centres. The 13C{1H}-NMR spectrum of 2 at
293 K as with 1, exhibits only one carbonyl resonance,
suggesting that all the carbonyl ligands are undergoing
rapid exchange on the NMR timescale at room
temperature.
The NMR spectrum of 3 is different from those of 1
and 2 as in this instance there are two different Ph2PH
1
environments. The H-NMR spectrum shows two dou-
blets [1JPH=343 and 349 Hz] in a 1:2 ratio for the PꢀH
protons, one centred at l 6.14 (iron-bonded Ph2PH)
and the other at l 6.04 (cobalt-bonded Ph2PH), respec-
Scheme 1. Products from the reaction of [Co2Fe(m3-S)(CO)9] with diphenylphosphine in a 1:1 ratio: (i) Ph2PH, 313 K, C7H8, 25 min.

J.D. King et al. / Journal of Organometallic Chemistry 642 (2002) 227–236
229
Table 1
Infrared, 1H- and 31P-NMR data for the new complexes 1–8
a
Compound w(CO) (cm−1
)
1H-NMR (l) b
31P-NMR (l) c
1
1
2
3
2081m, 2033vs, 2014s, 7.6–7.4 [m, 10H, Ph], 6.13 [d, 1H, JPH 361,
1883w, 1959w Co-PPh2H]
2049s, 2009vs, 1988sh, 7.6–7.1 [m, 20H, Ph], 5.99 [d, 2H, JPH 356,
1943m Co-PPh2H]
2020s, 1978vs, 1960s, 7.7–7.1 [m, 30H, Ph], 6.14 [d, 1H, JPH 343,
15.4 [s, Co-PPh2H]
1
15.3 [s, Co-PPh2H]
1
44.7 [s, Fe-PPh2H], 17.7 [s, br, Co-PPh2H]
1
1900w
Fe-PPh2H], 6.04 [d, 2H, JPH 349, Co-PPh2H]
4
5
2046m, 2005s, 1961w 7.6–7.3 [m, 20H, Ph]
226.2 [m-PPh2]
224.8 [s, br, m-PPh2], 206.2 [s, br, m-PPh2], 34.4 [s,
br, Co-PPh2H]
230.6 [s, br, m-PPh2], 194.6 [s, br, m-PPh2],
−112.0 [s, br, Co-PPhMe2]
91.0 [s, br, m-PPh2], −47.7 [d, Ph2PS, JPP 73]
1
2048w, 2017m,
1988s,1972s, 1945w
2047s, 2019m,
7.8–7.1 [m, 30H, Ph], 6.42 [dd, 1H, JPH 364,
3JPH4.7, Ph2PH]
2
5%
6
7.7–7.2 [m, 25H, Ph], 1.62 [d, 3H, JPH 9.5,
1988s,1973s, 1948w
PhPMeaMeb], 1.35 [d, 3H, 2J) 9.7, PhPMeaMeb]
2
2059w, 2039s, 2010s, 7.9–7.3 [m, 20H, Ph]
1993sh
7a
7b
8
2055s, 2017vs, 2000s, 7.7–7.3 [m, 10H, Ph], 3.56 [br, 1H, CH2], 3.42 [br, 36.9 [s, Ph2PCH2Sme]
1946w
1H, CH2], 2.34 [s, 3H, Me]
7.7–7.3 [m, 15H, Ph], 3.82 [dd,
gem
2
2055s, 2018vs,
1999s,1946w
2058s, 2021vs,
2006s,1950w
J
11.5, JPH 32.3 [s, Ph2PCH2SPh]
HH
2
6.6, 1H, CH2], 3.71 [dd, JPH 9.2, 1H, CH2]
7.8–7.3 [m, 10H, Ph], 2.71 [s, 3H, SMe]
63.9 [s, Ph2PC(SMe)ꢁS]
a Recorded in n-hexane solution.
b 1H chemical shifts (l) in ppm relative to SiMe4 (0.0 ppm), coupling constants in Hz in CDCl3 at 293 K.
c 31P chemical shifts (l) in ppm relative to 85% external H3PO4 (0.0 ppm) (upfield shifts negative). Spectra were {1H}-gated decoupled and
measured in CDCl3 at 293 K.
Scheme 2. Reagents and conditions: (i) 353 K, C7H8, 20 h; (ii) Ph2PH, 313 K, C7H8, 20 h; (iii) PhPMe2, 313 K, C7H8, 45 min; (iv) CO (70 atm.),
423 K, C7H8, 2 h.
tively. In the 31P{1H}-NMR spectrum of 3, there is a
sharp singlet at l 44.7 corresponding to the iron-bound
Ph2PH, and a broad resonance at l 17.7 corresponding
to the two cobalt-bound Ph2PH ligands. As with the
spectra for 1 and 2, the 13C{1H}-NMR spectrum of 3
shows only one carbonyl resonance at 293 K.
certain whether PꢀH bond cleavage could be achieved.
On heating either 1 or 2 at 353 K in toluene over 16 h
green crystalline [Co2Fe(m3-S)(m-PPh2)2(CO)6] 4 and
green–brown [Co2Fe(m3-S)(m-PPh2)2(CO)5(PPh2H)]
5
were obtained in similar yields [25% 4, 4–8% 5] for
both reactions. An improved yield of 5 was achieved by
treatment of 4 with Ph2PH in toluene at 313 K (82%).
Similarly, the tertiary phosphine analogue of 5,
[Co2Fe(m3-S)(m-PPh2)2(CO)5(PPhMe2)] 5%, was formed
in near quantitative yield from the reaction of 4 with
PhPMe2 at ambient temperature (Scheme 2).
2.2. Thermolyses of 1 and 2
The thermolyses of [Co2Fe(m3-S)(CO)8(PPh2H)] 1 and
[Co2Fe(m3-S)(CO)7(PPh2H)2] 2 were carried out to as-

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J.D. King et al. / Journal of Organometallic Chemistry 642 (2002) 227–236
1
Table 2
Complexes 4, 5 and 5% were characterised by IR, H,
,
Selected bond lengths (A) and angles (°) for species [Co2Fe(m3-S)(m-
31P, 13C-NMR spectroscopy and by mass spectrometry
and microanalysis (Table 1 and Section 3). In addition,
5% has been the subject of a single crystal X-ray struc-
ture determination.
PPh2)2(CO)5(PPhMe2)] 5%
Bond lengths
Co(1)ꢀCo(2)
Co(1)ꢀS
Co(1)ꢀP(3)
Co(2)ꢀS
FeꢀS
FeꢀP(2)
C(2)ꢀC(3)
2.526(1)
2.153(2)
2.173(2)
2.177(2)
2.266(2)
2.258(2)
1.454(4)
Co(1)ꢀFe
Co(1)ꢀP(1)
Co(2)ꢀFe
Co(2)ꢀP(2)
FeꢀP(1)
Co(1)ꢀC(4)
Co(1)ꢀC(6)
2.575(1)
2.155(2)
2.539(1)
2.178(2)
2.247(2)
2.086(3)
1.728(3)
A partial determination of the molecular structure of
complex 4 was made [13], but the poor quality of the
data precludes discussion of the structural details. The
X-ray analysis is, however, consistent with the pro-
posed structure. Furthermore, the spectroscopic proper-
ties of 4 are in agreement with the solid state structure
being maintained in solution. In the 31P{1H}-NMR
spectrum, a single broad resonance is observed at l
226.2 consistent with the two bridging phosphido
groups being equivalent. The 13C{1H}-NMR spectrum
recorded at 293 K clearly shows two triplets with
2JPC=12.6 and 1.7 Hz corresponding to the axial and
equatorial iron-bound CO ligands (non-fluxional at
room temperature). The cobalt-bound carbonyl groups
appear as broad signals centred at l 209.6 and 204.7,
implying that the axial carbonyls do not exchange at
room temperature with the equatorial carbonyls. This
observation suggests that the presence of the two bridg-
ing phosphido groups in some way discourages any
fluxional process involving exchange of carbonyls be-
tween metal centres, which might otherwise be opera-
tional at room temperature. It is noteworthy that in the
complex [Co2Fe(m-PPh2)2(m-CO)(CO)7], which differs
from 1 only in that it lacks a capping sulphur atom, all
eight carbonyls can interchange readily at room tem-
perature [14]. Clearly the capping sulphur atom plays a
role in inhibiting intramolecular carbonyl exchange at
room temperature. The absence of localised site ex-
change may be due to the bridging phosphido groups
CꢀO (carbonyl) 1.167–1.191
Bond angles
FeꢀCo(1)ꢀCo(2)
SꢀCo(1)ꢀFe
P(1)ꢀCo(1)ꢀFe
59.7(1)
56.4(1)
55.9(1)
SꢀCo(1)ꢀCo(2)
P(1)ꢀCo(1)ꢀCo(2) 115.5(1)
P(1)ꢀCo(1)ꢀS
P(3)ꢀCo(1)ꢀFe
P(3)ꢀCo(1)ꢀP(1)
54.8(1)
90.3(1)
144.2(1)
104.1(1)
P(3)ꢀCo(1)ꢀCo(2) 130.6(1)
P(3)ꢀCo(1)ꢀS
SꢀCo(2)ꢀFe
98.9(1)
56.8(1)
56.6(1)
52.3(1)
52.6(1)
85.1(1)
53.6(1)
164.7(1)
69.8(1)
71.2(1)
61.1(1)
P(2)ꢀCo(2)ꢀCo(1) 117.3(1)
P(2)ꢀCo(2)ꢀFe
SꢀFeꢀCo(1)
P(1)ꢀFeꢀCo(1)
P(1)ꢀFeꢀS
P(2)ꢀFeꢀCo(2)
P(2)ꢀFeꢀP(1)
FeꢀP(2)ꢀCo(2)
FeꢀSꢀCo(1)
Co(2)ꢀFeꢀCo(1)
SꢀFeꢀCo(2)
P(1)ꢀFeꢀCo(2)
P(2)ꢀFeꢀCo(1)
P(2)ꢀFeꢀS
Co(2)ꢀSꢀCo(1)
FeꢀSꢀCo(2)
SꢀCo(2)ꢀCo(1)
FeꢀP(1)ꢀCo(1)
59.2(2)
53.5(1)
111.7(1)
112.5(1)
81.9(1)
71.4(1)
69.7(1)
53.9(1)
71.6(1)
FeꢀCo(2)ꢀCo(1)
inhibiting any twist of the carbonyls at the metal cen-
tres, which has been shown to be involved in the
process of exchange in dicobalt alkyne-bridged species
[15].
Suitable crystals of 5% for X-ray diffraction (XRD)
study were grown by diffusion of hexane into a
dichloromethane solution of 5% at 253 K. The structure
is shown in Fig. 1, selected bond distances and angles
are given in Table 2.
The molecule consists of a triangle of metal atoms,
Co2Fe, capped by a sulphur atom to give a pseudote-
trahedral core. Similar cores have been identified for a
number of crystallographically characterised complexes
[7,12,16] including [Co2Fe(m3-S)(CO)9] [16a] and
[Co2Fe{m3-S(Cr(CO)5)}(CO)9] [16b]. In addition, each
FeꢀCo bond is bridged equatorially by a diphenylphos-
phido group with the FeꢀP distances [2.247(2), 2.258(2)
,
,
A] being longer than the CoꢀP [2.155(2), 2.178(2) A]
distances. Two carbonyl groups complete the co-ordi-
nation spheres of Fe and Co(2), while for Co(1), a
carbonyl and a PPhMe2 ligand, the latter of which
occupies an equatorial site. The increased steric de-
mands imposed by the 7-coordinate iron atom may
partly explain the relatively long FeꢀP distances (vide
supra), along with the elongated FeꢀS distance [2.266(2)
,
A] as compared with the corresponding CoꢀS sulphur
,
distances [2.153(2), 2.177(2) A] and the average metal–
,
sulphur distance [2.139(4) A] in [Co2Fe(m3-S)(CO)9].
The spectroscopic properties of 5% are in accordance
Fig. 1. Molecular structure of 5% including the atom numbering
scheme. Hydrogen atoms have been omitted for clarity.
with the solid state structure being maintained in solu-

J.D. King et al. / Journal of Organometallic Chemistry 642 (2002) 227–236
231
tion. Furthermore, on the basis of the close similarity of
the spectroscopic properties of 5%–5, a similar structure
may be ascribed to 5 (Scheme 2). In the 1H-NMR
spectrum of 5, in addition to phenyl resonances, a
dination of the phosphorus centre to iron rather than
cobalt. In the 13C{1H}-NMR spectrum, in addition to
aromatic resonances, four carbonyl resonances are ob-
served at l 209.7, 205.0, 199.8 and 198.2. The first of
these is a sharp signal and is ascribed to the iron-bound
carbonyls while the three more upfield resonances are
broad and are assigned to the cobalt-bound carbonyls;
one of these three upfield signals is due to the three
carbonyls bound to the same cobalt and there are two
separate resonances for the inequivalent carbonyl lig-
ands on the other cobalt atom. We cannot entirely rule
out the formulation of complex 6 as [Co2Fe(m3-S)(m-
PPh2)2(CO)7], which would require the scission of an
FeꢀCo edge, as this also complies with the EAN rule.
However, the sharpness of one of the PPh2 signals [l
−47.7] suggests that one phosphido group is attached
only to the iron atom confirming the structure shown in
Scheme 2 as the more likely.
1
doublet of doublets centred at l 6.42 with JPH=364
3
Hz and JPH=4.7 Hz is assigned to the PꢀH proton of
the diphenylphosphine ligand. Complex 5% also exhibits
phenyl resonances and, in addition, shows a pair of
doublets corresponding to the inequivalent methyl
2
groups, with coupling constants JPH=9.5 and 9.7 Hz.
In the 31P{1H}-NMR spectrum of 5, there are three
broad singlets, two in the bridging phosphido group
region [l 224.8 and 206.2] and one signal which is
further upfield [l 34.4] and corresponds to the terminal
secondary phosphine ligand. The broadness of the upfi-
eld signal provides further evidence that the phosphine
is bound to a quadrupolar cobalt centre. A similar
31P{1H}-spectrum is found for 5% with resonances ap-
pearing at l 230.6, 194.6 and 28.2.
While substitution of a cobalt-bound carbonyl group
occurs on reaction of 4 with Ph2PH or PhPMe2 treat-
ment of 4 with 70 atm. of CO at 423 K results in the
formation of [Co2Fe(m3-SPPh2)(m-PPh2)(CO)7] 6 as the
sole product in 28% yield. Although single crystals for
6 suitable for XRD could not be obtained, the spectro-
scopic and analytical data are consistent with the struc-
ture depicted in Scheme 2. The FAB mass spectrum
displays a molecular ion peak and fragmentation peaks
corresponding to the loss of up to seven carbonyl
groups. In the 31P{1H}-NMR spectrum, two resonances
are observed; the downfield resonance [l 91.0] is broad
and is assigned to a phosphido group bridging an
FeꢀCo edge, the broadness being attributed to the
presence of the quadrupolar cobalt centre. The more
upfield resonance [l −47.7] takes the form of a sharp
2.3. Deprotonation and reaction of 1 with electrophiles
The complex [Co2Fe(m3-S)(CO)8(PPh2H)] 1 can be
deprotonated readily using one equivalent of n-BuLi in
THF at 195 K. The resulting anion (presumably
[Co2Fe(m3-S)(CO)8(PPh2Li)] or an oligomer based on
this formula) was used for further reactions without
purification. Reformation of 1 by treatment of the
anion with HBF4·OEt2 proceeded in good yield
(Scheme 3).
2.3.1. Addition of RSCH2Cl (R=Me, Ph)
An excess of a chlorothiomethane, RSCH2Cl (R=
Me, Ph), was added to a solution of the lithium salt of
1 and the solution stirred at 333 K for 2 h to give
[Co2Fe(m3-S)(m-PPh2CH2SR)(CO)8] (R=Me 7a, Ph 7b),
respectively, in good yield. Complexes 7a and 7b have
been previously synthesised in similar yields by the
2
doublet with JPP=73 Hz and is assigned to the Ph2PS
ligand, the sharpness of the signal supporting the co-or-
Scheme 3. Reagents and conditions: (i) n-BuLi, THF, 195 K; (ii) HBF4·OEt2, THF, 293 K; (iii) RSCH2Cl, THF, 333 K; (iv) xs. CS2, THF, 293
K; (v) xs. MeI, THF, 293 K.

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J.D. King et al. / Journal of Organometallic Chemistry 642 (2002) 227–236
crystal XRD study. Crystals of 8 suitable for an X-ray
structural analysis were grown by diffusion of pentane
into a dichloromethane solution of 8 at 253 K. A view
of the structure of 8 is shown in Fig. 2; selected bond
distances and angles are listed in Table 3.
The structure comprises a Co2Fe triangle capped by a
m3-S ligand with the CoꢀCo edge equatorially bridged
by a bidentate Ph2PC(SMe)ꢁS ligand. The phospho-
rus–sulphur ligand s-bonds to the metal centres via the
phosphorus and the doubly bonded sulphur atoms and
is incorporated into a twisted CoꢀPꢀCꢁSꢀCo dimetalla-
cycle. The Co(1)ꢀCo(2)ꢀS(2)ꢀC(2) unit is planar to
,
,
within 0.1 A with P(1) displaced 0.63 A from this plane
in the opposite direction to S(1). The co-ordination
spheres of the metal atoms are completed by carbonyl
ligands, two on each cobalt (equatorial and axial) and
three on iron (two equatorial and one axial).
Fig. 2. Molecular structure of 8 including the atom numbering
scheme. Hydrogen atoms have been omitted for clarity.
Within the core, the bond lengths compare closely
with 7b [7]. Both of the CoꢀFe bond lengths in 8 are
,
2.536(2) A which compares closely with the mean value
Table 3
,
found in 7b [the corresponding values are 2.544(2) and
Selected bond lengths (A) and angles (°) for species [Co2Fe(m3-S){m-
PPh2C(SMe)ꢁS}(CO)8] 8
,
2.528(2) A]. The CoꢀCo distances do differ significantly
,
,
[2.503(1) A (8) cf. 2.528(2) A (7b)] and this is pre-
sumably due to the constraints imposed by the bridging
ligand. This difference can be attributed to the fact that
in 7b, the bridging ligand contains a singly bonded
PꢀCꢀS unit, whilst in 8, the corresponding unit contains
a CꢁS double bond. Despite the PꢀCꢀS angle being
greater for 8 [118.1(5)°] as compared with 7b [111.4(4)°]
Bond lengths
Co(1)ꢀCo(2)
Co(1)ꢀS
Co(2)ꢀFe
Co(2)ꢀS(2)
S(1)ꢀC(2)
S(2)ꢀC(2)
2.503(1)
2.161(2)
2.536(1)
2.242(3)
1.699(9)
1.651(9)
Co(1)ꢀFe
Co(1)ꢀP(1)
Co(2)ꢀS
FeꢀS
S(1)ꢀC(1)
P(1)ꢀC(2)
2.536(2)
2.207(2)
2.173(2)
2.167(3)
1.790(9)
1.840(7)
CꢀO (carbonyl) 1.131–1.151
,
the shorter CꢀS bond in 8 [1.651(9) A vs. 1.809(9) 7b] is
Bond angles
sufficient to shorten the CoꢀCo distance.
FeꢀCo(1)ꢀCo(2)
SꢀCo(1)ꢀFe
P(1)ꢀCo(1)ꢀFe
FeꢀCo(2)ꢀCo(1)
SꢀCo(2)ꢀFe
S(2)ꢀCo(2)ꢀFe
Co(2)ꢀFeꢀCo(1)
SꢀFeꢀCo(2)
FeꢀSꢀCo(1)
C(1)ꢀS(1)ꢀC(2)
C(2)ꢀP(1)ꢀCo(1) 112.8(3)
P(1)ꢀC(2)ꢀS(1) 117.4(5)
60.4(1)
54.2(1)
149.2(1)
60.4(1)
54.1(1)
149.2(1)
59.1(1)
54.4(1)
71.8(1)
103.5(5)
SꢀCo(1)ꢀCo(2)
P(1)ꢀCo(1)ꢀCo(2)
P(1)ꢀCo(1)ꢀS
SꢀCo(2)ꢀCo(1)
S(2)ꢀCo(2)ꢀCo(1) 100.6(1)
S(2)ꢀCo(2)ꢀS
SꢀFeꢀCo(1)
Co(2)ꢀSꢀCo(1)
FeꢀSꢀCo(2)
C(2)ꢀS(2)ꢀCo(2)
S(2)ꢀC(2)ꢀS(1)
P(1)ꢀC(2)ꢀS(2)
55.0(1)
89.2(1)
105.9(1)
54.5(1)
Only two crystallographically characterised com-
plexes have been reported featuring the Ph2PC(SMe)ꢁS
group acting as a bridging ligand [18]. Notably, in 8,
the ligand bridges in a h1(P):h1(S) mode differing from
the previously observed h1(P):h1(C):h1(S) mode in
which the CꢁS bond p-bonds to one of the metal
centres. Furthermore, 8 is the first example of a ligand
of this type bridging metal centres linked by a metal–
metal bond.
95.3(1)
54.0(1)
70.5(1)
71.5(1)
109.0(3)
124.4(4)
118.1(5)
Complex 8 was also characterised by mass spec-
trometry (MS) and by 1H, 31P, 13C-NMR and IR
spectroscopy and these techniques confirm the results of
the X-ray determination. In the 1H-NMR spectrum,
there is a multiplet resonance in the phenyl region and
a singlet methyl group resonance (l 2.71), whilst in the
31P{1H}-NMR spectrum there is a broad singlet at l
63.9. The 13C{1H}-NMR spectrum shows a singlet for
the three iron-bound carbonyls consistent with localised
site exchange [10]. The Co-bound carbonyls are not
clearly visible due to the quadrupolar broadening of
reaction of [Co2Fe(m3-S)(CO)9] with the pre-prepared
Ph2PCH2SR (R=Me, Ph) ligands. The X-ray structure
of 7b reveals the CoꢀCo bond to be bridged equatori-
ally by the Ph2PCH2SPh ligand [7].
2.3.2. Addition of CS2 followed by MeI
An excess of carbon disulphide was added to the
lithium salt of 1 and the resulting anion (presumably
[Co2Fe(m3-S)(CO)8(PPh2CS2Li)] [17]) was methylated
with methyl iodide to give [Co2Fe(m3-S){m-
PPh2C(SMe)ꢁS}(CO)8] 8 in good yield. Complex 8 has
been characterised spectroscopically (Table 1 and Sec-
tion 3) and, in addition, has been the subject of a single
their resonances. The central carbon of the bridging
1
ligand is observed as a doublet at l 132.7 with JPC
=
52 Hz. A doublet is also observed at l 32.7 with
3JPC=7 Hz.

J.D. King et al. / Journal of Organometallic Chemistry 642 (2002) 227–236
233
3. Conclusions
[Co2Fe(m3-S)(CO)6(PPh2H)3] 3 (0.021 g, 4%). 1 Anal.
Found: C, 38.63; H 1.71; P 4.46. C20H11O8Co2FePS
Calc.: C, 38.99; H, 1.80; P 5.03%. FABMS 616 [M+],
M+−n(CO) (n=1–8). 13C-NMR (1H composite pulse
decoupled, CDCl3 at 293 K): l 202.5 [s, 8CO] and
133–126 [m, Ph]. 2 Anal. Found: C, 47.73; H 2.73; P
7.93. C31H22Co2FeO7P2S Calc.: C, 48.09; H, 2.86; P
8.00%. FABMS 774 [M+], M+-n(CO) (n=1–7). 13C-
NMR (1H composite pulse decoupled, CDCl3 at 293
K): l 209.4 [s, 7CO] and 133–128 [m, Ph]. 3 Anal.
Found: C, 53.94; H 3.52; P 9.81. C42H33Co2FeO6P3S
Calc.: C, 54.10; H, 3.57; P 9.97%. FABMS 932 [M+],
M+−n(CO) (n=1–6). 13C-NMR (1H composite pulse
decoupled, CDCl3 at 293 K): l 212.6 [s, 6CO] and
134–128 [m, Ph].
The co-ordinated diphenylphosphine unit in 1 has
been shown to be susceptible to PꢀH bond cleavage,
either through the use of basic conditions or by ther-
molysis leading to oxidative addition. Once the PꢀH
bond has been cleaved, various further reactions can
take place either involving elimination of hydrogen to
give the phosphido-bridged complexes (4, 5) or attack
by electrophilic reagents to give the modified phosphine
ligands (7, 8).
4. Experimental
4.1. General techniques
4.3. Reaction of [Co2Fe(v3-S)(CO)8(PPh2H)] 1 with
All reactions were carried out under an atmosphere
of dry, oxygen-free nitrogen, using standard Schlenk
techniques. Solvents were distilled under nitrogen from
appropriate drying agents and degassed prior to use
[19]. Infrared spectra were, unless otherwise stated,
recorded in hexane solution in 0.5 mm NaCl cells, using
a Perkin–Elmer 1710 Fourier-transform spectrometer.
Fast atom bombardment (FAB) mass spectra were
recorded on a Kratos Concept instrument using 3-ni-
trobenzyl alcohol as a matrix. Proton (reference to
SiMe4), 31P- and 13C-NMR spectra were recorded on
either a Bruker WM250 or AM400 spectrometer, 31P-
NMR chemical shifts are referenced to 85% H3PO4; all
spectra were recorded in CDCl3. Preparative thin-layer
chromatography (TLC) was carried out on commercial
Merck plates with a 0.25 mm layer of silica, or on 1
mm silica plates prepared at the University Chemical
Laboratory, Cambridge. Column chromatography was
performed on Kieselgel 60 (70–230 or 230–400 mesh).
Products are given in order of decreasing Rf values.
Elemental analyses were performed at the University
Chemical Laboratory, Cambridge.
Ph2PH
To a solution of [Co2Fe(m3-S)(CO)8(PPh2H)] 1 (1.0 g,
1.62 mmol) in toluene (50 cm3) was added a solution of
Ph2PH (0.272 g, 1.46 mmol) in toluene (10 cm3). The
solution was stirred at 313 K for 3 h. After removal of
the solvent under reduced pressure, the mixture was
purified by flash column chromatography with hexane–
dichloromethane (4:1) as eluent. This gave brown crys-
talline [Co2Fe(m3-S)(CO)7(PPh2H)2] 2 (0.988 g, 79%)
and brown [Co2Fe(m3-S)(CO)6(PPh2H)3] 3 (0.120 g,
8%).
4.4. Thermolysis of [Co2Fe(v3-S)(CO)8(PPh2H)] (1)
A solution of [Co2Fe(m3-S)(CO)8(PPh2H)] 1 (0.490 g,
0.66 mmol) in THF (50 cm3) was stirred at 353 K for a
period of 17 h. After removal of solvent under reduced
pressure, the residue was purified by flash chromatogra-
phy with hexane–dichloromethane (9:1) as eluent. This
gave some starting material, green crystalline
[Co2Fe(m3-S)(m-PPh2)2(CO)6] 4 (0.122 g, 25%) and green
Unless otherwise stated, all reagents were obtained
from commercial suppliers and used without further
purification. The synthesis of [Co2Fe(m3-S)(CO)9] has
been reported previously [20].
crystalline
[Co2Fe(m3-S)(m-PPh2)2(CO)5(PPh2H)]
5
(0.034 g, 6%). 4 Anal. Found: C, 48.23; H, 2.78.
C30H20Co2FeO6P2S Calc.: C, 48.42; H, 2.71%. FABMS
744 [M+], M+-n(CO) (n=1–6). 13C-NMR (1H com-
posite pulse decoupled, CDCl3 at 293 K): l 213.8 [t,
2
4.2. Reaction of [Co2Fe(v3-S)(CO)9] with Ph2PH
2JPC 13, FeCO], 211–208 [br, 2CoCO], 206.7 [t, JPC
13, FeCO], 206–204 [br, 2CoCO] and 143–128 [m, Ph].
To a solution of [Co2Fe(m3-S)(CO)9] (0.250 g, 0.55
mmol) in toluene (30 cm3) was added a solution of
Ph2PH (0.102 g, 0.55 mmol) in toluene (10 cm3). The
solution was stirred at 313 K for 25 min. After removal
of the solvent under reduced pressure, the mixture was
purified using preparative TLC with hexane–
dichloromethane (4:1) as eluent. This gave, in addition
to a trace of the starting complex, brown crystalline
[Co2Fe(m3-S)(CO)8(PPh2H)] 1 (0.193 g, 57%), brown
[Co2Fe(m3-S)(CO)7(PPh2H)2] 2 (0.024 g, 8%) and brown
5
Anal. Found: C, 54.79;
H
3.70;
P
10.05.
C41H31Co2FeO5P3S Calc.: C, 54.57; H, 3.46; P 10.30%.
FABMS 902 [M+], M+-n(CO) (n=1–5). 13C-NMR
(1H composite pulse decoupled, CDCl3 at 293 K): l
205.4 [br, 5CoCO] and 134–128 [m, Ph].
4.5. Thermolysis of [Co2Fe(v3-S)(CO)7(PPh2H)2] (2)
A solution of [Co2Fe(m3-S)(CO)7(PPh2H)2] (2) (1.250
g, 1.61 mmol) in toluene (50 cm3) was stirred at 353 K

234
J.D. King et al. / Journal of Organometallic Chemistry 642 (2002) 227–236
for 20 h. After the solvent was removed under reduced
pressure, the mixture was purified by flash column
chromatography with hexane–dichloromethane (9:1) as
eluent. This gave brown crystalline [Co2Fe(m3-
S)(CO)8(PPh2H)] 1 (0.277 g, 23%), green crystalline
4.8. Reaction of [Co2Fe(v3-S)(CO)8(PPh2H)] 1 with
n-BuLi and RSCH2Cl (R=Me, Ph)
4.8.1. R=Me
To a solution of [Co2Fe(m3-S)(CO)8(PPh2H)] 1 (0.300
g, 0.49 mmol) in THF (40 cm3) at 195 K was added
n-BuLi (0.3 cm3, 0.49 mmol) in hexane. The mixture
was allowed to warm to room temperature (r.t.), after
which an excess of MeSCH2Cl (0.82 cm3, 0.98 mmol)
was added. The resulting solution was stirred at 333 K
for 2 h and then filtered through silica. After removal
of the volatiles under reduced pressure, TLC separation
with hexane–ethylacetate (5:1) gave a trace of starting
material followed by green crystalline [Co2Fe(m3-S)(m-
PPh2CH2SMe)(CO)8] (7a) (0.164 g, 52%). 7a FABMS
648 [M+], M+-n(CO) (n=1–7). 13C-NMR (1H com-
posite pulse decoupled, CDCl3 at 293 K): l 212.9 [s,
3Fe−CO], 199.5 [br, 4CoCO], 135–128 [m, Ph], 48.0
[CO Fe(m3-S)(m-PPh2)2(CO)6] 4 (0.304 g, 25%), unre-
2
acted starting material, green crystalline [Co2Fe(m3-
S)(m-PPh2)2(CO)5(PPh2H)] 5 (0.118 g, 8%) and a trace
of crystalline [Co2Fe(m3-S)(CO)6(PPh2H)3] 3.
4.6. Reaction of [Co2Fe(v3-S)(v-PPh2)2(CO)6] 4 with
Ph2PH or PhPMe2
4.6.1. With Ph2PH
To a solution of [Co2Fe(m3-S)(m-PPh2)2(CO)6] 4
(0.200 g, 0.27 mmol) in toluene (30 cm3) was added
Ph2PH (0.050 g, 0.27 mmol) and the mixture stirred at
313 K for 2 h. After the removal of solvent under
reduced pressure, the residue was purified by column
chromatography, eluting with hexane–dichloromethane
(4:1), to yield green crystalline [Co2Fe(m3-S)(m-PPh2)2-
(CO)5(PPh2H)] 5 (0.199 g, 82%).
1
[d, JPC 19, CH22] and 27.7 [s, SMe].
4.8.2. R=Ph
To a solution of [Co2Fe(m3-S)(CO)8(PPh2H)] 1 (0.300
g, 0.49 mmol) in THF (40 cm3) at 195 K was added
n-BuLi (0.3 cm3, 0.49 mmol) in hexane. The mixture
was allowed to warm to r.t., after which an excess of
PhSCH2Cl (0.13 cm3, 0.98 mmol) was added. The re-
sulting solution was stirred at 333 K for 2 h and then
filtered through silica. After removal of the volatiles
under reduced pressure, TLC separation with hexane–
ethylacetate (5:1) gave a trace of starting material fol-
lowed by green crystalline [Co2Fe(m3-S)(m-PPh2CH2-
SPh)(CO)8] 7b (0.224 g, 65%). 7b FABMS 710 [M+],
M+-n(CO) (n=1–7). 13C-NMR (1H composite pulse
decoupled, CDCl3 at 293 K): l 212.8 [s, 3Fe-CO], 200.0
4.6.2. With PhPMe2
To a solution of [Co2Fe(m3-S)(m-PPh2)2(CO)6] 4
(0.250 g, 0.34 mmol) in toluene (30 cm3) was added
PhPMe2 (0.046 g, 0.34 mmol) and the mixture stirred at
293 K for 45 min. After the removal of solvent under
reduced pressure, the residue was purified by column
chromatography, eluting with hexane–dichloromethane
(4:1), to yield green crystalline [Co2Fe(m3-S)(m-PPh2)2-
(CO)5(PPhMe2)] 5% (0.244 g, 85%). 5% FABMS 854
[M+], M+−n(CO) (n=1–5).
1
[br, 4CoCO], 134–128 [m, Ph] and 49.4 [d, JPC 17,
CH22].
4.9. Reaction of [Co2Fe(v3-S)(CO)8(PPh2H)] 1 with
n-BuLi, CS2 and MeI
4.7. Carbonylation of [Co2Fe(v3-S)(v-PPh2)2(CO)6] 4
To a solution of [Co2Fe(m3-S)(CO)8(PPh2H)] 1 (0.425
g, 0.69 mmol) in THF (40 cm3) at 195 K was added
n-BuLi (0.4 cm3, 0.49 mmol) in hexane. The mixture
was allowed to warm to r.t., after which a 5-fold excess
of CS2 (0.262 g, 3.45 mmol) was added. The resulting
solution was stirred at 293 K for 3 h, after which an
excess of MeI (0.490 g, 3.35 mmol) was added. After
further stirring at ambient temperature for 1 h, removal
of the volatiles under reduced pressure, followed by
TLC separation with hexane–dichloromethane (7:3) as
eluent, gave the purple crystalline complex [Co2Fe(m3-
S){m-PPh2C(SMe)ꢁS}(CO)8] 8 (0.252 g, 54%). 8 Anal.
Found: C, 36.83; H 1.82; P 4.51. C21H13Co2FeO7PS3
Calc.: C, 37.19; H, 1.93; P 4.57%. FAB MS 678 [M+],
M+−n(CO) (n=1–7). 13C-NMR (1H composite pulse
decoupled, CDCl3 at 293 K): l 212.6 [s, 3FeCO], 205.0
A solution of [Co2Fe(m3-S)(m-PPh2)2(CO)6] (4) (0.420
g, 0.56 mmol) in toluene (70 cm3) was added to a Roth
autoclave (100 cm3) and pressurised with CO (70 atm).
The sealed system was stirred at 423 K for 2 h. After
removal of the solvent under reduced pressure, the dark
red residue was redissolved in the minimum quantity of
dichloromethane, adsorbed onto silica and chromato-
graphically separated, eluting with hexane–dichloro-
methane (19:1) to give red [Co2Fe(m3-SPPh2)(m-
PPh2)(CO)7] 6 (0120 g, 28%) and a trace of starting
material. 6 FABMS 772 [M+], M+-n(CO) (n=1–7).
13C-NMR (1H composite pulse decoupled, CDCl3 at
293 K): l 209.7 [s, 2Fe−CO], 205.0 [br, 3CoCO],
199.8 [br, 1CoCO], 198.2 [br, 1CoCO] and 145–128 [m,
Ph].

J.D. King et al. / Journal of Organometallic Chemistry 642 (2002) 227–236
235
1
5. Supplementary material
[br, CoCO], 134–128 [m, Ph], 132.7 [d, JPC 52,
Ph2PC(SMe)ꢁS] and 32.7 [d, JPC 7, SMe].
3
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC nos. 168019–168020. Copies of
this information may be obtained free of charge from:
The Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (Fax: +44-1223-336033; e-mail: deposit@
ccdc.cam.ac.ul or www: http://www.ccdc.cam.ac.uk).
4.10. Crystal structure determinations of complexes
5% and 8
X-ray intensity data were collected with graphite-
,
monochromated Mo–Ka radiation (u=0.71073 A) ra-
diation, on a PW1100 four-circle diffractometer at
293(2) K for 5% and 8. Details of data collection,
refinement and crystal data are listed in Table 4.
Lorentz-polarisation and absorption corrections were
applied to the data of all the compounds. The positions
of the metal atoms were deduced from Patterson syn-
theses. The remaining non-hydrogen atoms were re-
vealed from subsequent difference-Fourier syntheses.
Refinement was based on F [21].
Acknowledgements
This work was supported by BP Chemicals, Sunbury
(to C.-Y.M.).
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Table 4
Crystal data and structure refinement parameters for complexes 5%
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5%
8
(d) P. Dunn, J.C. Jeffery, P. Sherwood, J. Organomet. Chem.
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Empirical formula
Formula weight
Crystal system
Space group
Unit cell dimensions
C
854.34
Triclinic
C1 (alt no. 2)
37H31Co2FeO5P3S C21H13Co2FeO7PS3
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Triclinic
(
(
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,
a (A)
22.667(5)
12.833(3)
13.520(3)
90.41(2)
107.53(3)
90.01(2)
3724(3)
4
1.52
1736
Black prism
0.36×0.36×0.38
3.00–25.00
−24 to 24, 0–16,
−15 to 15
6844
11.060(4)
12.365(4)
10.924(4)
90.55(1)
95.284(1)
115.99(1)
1342(1)
2
1.68
676
,
b (A)
,
c (A)
a (°)
i (°)
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k (°)
3
,
U (A )
Z
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m(Mo–Ka) (mm−1
F(000)
)
Colour, habit
Crystal size (mm)
q-range (°)
Black prism
0.32×0.27×0.38
3.00–25.00
−12 to 12, −14 to
14, 0–11
4981
Limiting hkl indices
Reflections collected
Independent reflections 4657 b
2859 b
2859/0/222
Data/restraints/
parameters
4657/0/191
Final R indices a
[I\2|(I)]
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R1=0.0684,
R%=0.0747
R=0.0503,
R%=0.0521
All data
Min. and max.
peak/hole (e A
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1.09 and −0.865
0.658 and −0.583
−3
,
)
a R1=ꢀꢁFoꢂ−ꢂFcꢁ/ꢀꢂFoꢂ, wR2=ꢀ [w(F2o−Fc2)2]/ꢀ[w(Fo2)2]2, w−1
=
[|2(Fo)2+(aP)2+bP] with a=0.0512 and b=2.8561 for 4, P=
[max(F2o, 0)+2(F2c)]/3.
b Weights of 1/|2(F) were applied; [I/|(I)\3]; R=ꢀ(DF)/ꢀ(Fo);
R%=[ꢀ(DF)2/ꢀw(Fo)2]2.

236
J.D. King et al. / Journal of Organometallic Chemistry 642 (2002) 227–236
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