Chemistry of the paramagnetic Co3 (CO)9(μ3-S) cluster. Rational synthesis of Co3(CO)7(μ-X)(μ3-S) complexes

Article abstract of DOI:10.1021/om980147n

The paramagnetic Co₃(CO)₉(μ₃-S) cluster (1) reacts with organic compounds containing S-H, S-S, or P-H bonds to give diamagnetic Co₃(CO)₇(μ-X)(μ₃-S) (μ-X = (μ-L, μ-(1,2-η)-L, and μ-(1,3-η)-L) complexes. The reaction was used to prepare the derivatives with μ-L = SR (2a-h; R = Et, t-Eu, CH₂Ph, allyl, Ph, C₆F₅, 2-naphthyl, CH₂CH₂OH) and PPh₂ (7), μ-(1,2-η)-L = P(S)Ph₂ (8), and μ-(1,3-η)-L = S₂CR(R = SMe (4), OMe (5), Ph (6)). The reaction results in an increase of the oxidation state of cobalt and may be therefore called an oxidative substitution. It is the first successful and rational way to prepare derivatives of Co₃(CO)₉-(μ₃-S), a fundamental cluster molecule described in 1961. The crystal structures of the triphenylphosphine-substituted derivative of 2b, Co₃(CO)₄(PPh₃) ₃(μ-S-t-Bu)(μ₃-S) (3), and of 4, 6, and 8 were determined. A new, high-yield synthesis of 1 is described.

Full text of DOI:10.1021/om980147n

4218
Organometallics 1998, 17, 4218-4225
Ch em istr y of th e P a r a m a gn etic Co3(CO)9(µ3-S) Clu ster .
Ra tion a l Syn th esis of Co3(CO)7(µ-X)(µ3-S) Com p lexes
Sa´ndor Vastag,† Giuliana Gervasio,*,‡ Domenica Marabello,‡
Ga´bor Szalontai,§ and La´szlo´ Marko´*,‡,|
Institute of Organic Chemistry and Central Laboratory, University of Veszpre´m, and
Research Group for Petrochemistry of the Hungarian Academy of Sciences, P.O. Box 158,
H-8201, Veszpre´m, Hungary, and Dipartimento di Chimica IFM, Universita` di Torino,
I-10125 Torino, Italy
Received March 2, 1998
The paramagnetic Co3(CO)9(µ3-S) cluster (1) reacts with organic compounds containing
S-H, S-S, or P-H bonds to give diamagnetic Co3(CO)7(µ-X)(µ3-S) (µ-X ) (µ-L, µ-(1,2-η)-L,
and µ-(1,3-η)-L) complexes. The reaction was used to prepare the derivatives with µ-L )
SR (2a -h ; R ) Et, t-Bu, CH2Ph, allyl, Ph, C6F5, 2-naphthyl, CH2CH2OH) and PPh2 (7),
µ-(1,2-η)-L ) P(S)Ph2 (8), and µ-(1,3-η)-L ) S2CR (R ) SMe (4), OMe (5), Ph (6)). The reaction
results in an increase of the oxidation state of cobalt and may be therefore called an oxidative
substitution. It is the first successful and rational way to prepare derivatives of Co3(CO)9-
(µ3-S), a fundamental cluster molecule described in 1961. The crystal structures of the
triphenylphosphine-substituted derivative of 2b, Co3(CO)4(PPh3)3(µ-S-t-Bu)(µ3-S) (3), and of
4, 6, and 8 were determined. A new, high-yield synthesis of 1 is described.
In tr od u ction
Na2[Fe(CO)4] to give Co2Fe(CO)9(µ3-S),7 (d) with CpW-
(CO)3AsMe2 to give the unusual tetranuclear cluster
CpW(CO)3Co2(µ3-S)(µ-AsMe2)2Co(CO)3,8 and (e) with
Me3NO and PhC2H to give Co4(CO)8(µ-CO)2(µ4-S) (µ4-
(1,2-η)-HC2Ph).9 These reactions, however, appear to
have nothing in common, and in addition those men-
tioned under (d) and (e) involve very complex and
stoichiometrically unclear transformations.
This behavior of 1 contrasts sharply with that of the
closely related diamagnetic Co2Fe(CO)9(µ3-S),10 which
has a rich chemistry, including substitution of the CO
ligands by phosphines11 and isonitriles,3 reversible
oxidation and reduction,4,12 transformations through
metal exchange and addition reactions into other tri-
nuclear7,8,13 (including chiral) and tetranuclear14 clus-
ters, and use as a ligand with sulfur as the donor atom.15
At the same time a large number of carbonyl clusters
are known which contain the Co3S pyramid as a
building block and can be regarded as substituted
derivatives of 1 with the general formula Co3(CO)7(µ-
The chemistry of the paramagnetic Co3(CO)9(µ3-S)
cluster (1),1 first prepared 37 years ago, is rather poorly
developed. The most obvious reactions in metal carbo-
nyl chemistry, the substitution of the CO ligands by
phosphines2 or isonitriles,3 result in decomposition. This
may be due to the fact that the “surplus” electron of 1
occupies a metal-metal antibonding orbital, and if CO
is replaced by a ligand which is a poorer π-acceptor than
CO, the effect of this antibonding orbital in decreasing
the stability of the cluster becomes more pronounced.
Although the removal of one electron from 1 by oxida-
tion results in the electron-precise [1]+ cation,4 this com-
plex also proved to be very labile and could be identified
only in solution. Attempts to prepare Co3(CO)9(µ3-S)M-
(CO)5 (M ) Cr, Mo, W) type complexes failed as well.2
Until now only a few reactions of 1 which lead to
stable molecules have been described: (a) with S8 to give
the hexanuclear [Co3(CO)7(µ3-S)]2S2,5 (b) with PhCH2-
SH etc. and the corresponding disulfides to give com-
pounds described as “Co3(CO)6(µ3-SR)(µ3-S)” (R ) Et,
CH2Ph) but not unequivocally characterized,6 (c) with
(6) Klumpp, E.; Marko´, L.; Bor, G. Chem. Ber. 1964, 97, 926.
(7) Honrath, U.; Vahrenkamp, H. Z. Naturforsch., B 1984, 39, 559.
(8) Richter, F.; Vahrenkamp, H. Chem. Ber. 1982, 115, 3224.
(9) Gambino, O.; Gervasio, G.; Prada, P.; Rossetti, R.; Stanghellini,
P. L. Inorg. Chem. 1988, 27, 4081.
(10) (a) Khattab, S. A..; Marko´, L.; Bor, G.; Marko´, B. J . Organomet.
Chem. 1964, 1, 373. (b) Stevenson, D. L.; Wei, C. H.; Dahl, L. F. J .
Am. Chem. Soc. 1971, 93, 6027. (c) Marko´, L..; Taka´cs, J . Inorg. Synth.
1989, 26, 245;.
† Institute of Organic Chemistry, University of Veszpre´m.
‡ Universita` di Torino.
§ Central Laboratory, University of Veszpre´m.
| Research Group for Petrochemistry of the Hungarian Academy of
Sciences.
(1) (a) Marko´, L.; Bor, G.; Klumpp, E. Chem. Ind. (London) 1961,
1491. (b) Wei, C. H.; Dahl, L. F. Inorg. Chem. 1967, 6, 1229. (c) Strouse,
C. E.; Dahl, L. F. Discuss. Faraday Soc. 1969, 47, 93.
(2) Marko´, L.; Vastag, S. Unpublished results.
(3) Newman, J .; Manning, A. R. J . Chem. Soc., Dalton Trans. 1974,
2549.
(4) (a) Honrath, U.; Vahrenkamp, H. Z. Naturforsch., B 1984, 39,
545. (b) Honrath, U.; Vahrenkamp, H. Z. Naturforsch., B 1984, 39,
555.
(11) (a) Burger, K.; Korecz, L.; Bor, G. Magy. Ke´m. Foly. 1968, 74,
542. (b) Aime, S.; Milone, L.; Rossetti, R.; Stanghellini, P. L. Inorg.
Chim. Acta 1977, 25, 103. (c) Rossetti, R.; Gervasio, G.; Stanghellini,
P. L. J . Chem. Soc., Dalton Trans. 1978, 222.
(12) Peake, B. M.; Rieger, P. H.; Robinson, B. H.; Simpson, J . Inorg.
Chem. 1981, 20, 2540.
(13) (a) Richter, F.; Vahrenkamp, H. Angew. Chem. 1978, 90, 916;
Angew. Chem., Int. Ed. Engl. 1978, 17, 864. (b) Fischer, K.; Deck, W.;
Schwarz, M.; Vahrenkamp, H. Chem. Ber. 1985, 118, 4946.
(14) Richter, F.; Vahrenkamp, H. Organometallics 1982, 1, 756.
(15) Richter, F.; Vahrenkamp, H. Angew. Chem. 1978, 90, 474;
Angew. Chem., Int. Ed. Engl. 1978, 17, 444.
(5) (a) Marko´, L.; Bor, G.; Klumpp, E.; Marko´, B.; Alma´sy, G. Chem.
Ber. 1963, 96, 955. (b) Stevenson, D. L.; Magnuson, V. R.; Dahl, L. F.
J . Am. Chem. Soc. 1967, 89, 3727.
S0276-7333(98)00147-2 CCC: $15.00 © 1998 American Chemical Society
Publication on Web 08/27/1998

Rational Synthesis of Co3(CO)7(µ-X)(µ3-S) Complexes
Organometallics, Vol. 17, No. 19, 1998 4219
Ta ble 1. In fr a r ed Sp ectr oscop ic Da ta for
X)(µ3-S). All of these complexes have been isolated,
however, from complex reaction mixtures obtained by
reacting Co2(CO)8 with different sulfur compounds.
They are formed in obviously very complicated reac-
tions, and the reaction paths leading to these com-
pounds are not clear at all. The bridging ligands X in
these complexes vary widely and include (1,2-η)-
SCSCCo3(CO)9,16 (1,3-η)-S2CCCo3(CO)9,17 (1,2-η)-S(Me)-
Co3(CO)7(µ-SR)(µ3-S) (Typ e 2) Com p lexes in th e νCO
Region , in Hexa n e Solu tion (cm -1
)
complex
R
ν1 (m) ν1 (vs) ν1 (s) ν1 (vw)
2087 2045 2026 2000
2088 2045 2024 2007 this work
2087 2046 2026 2000
2088 2048 2026 2001 this work
2090 2047 2028 2010 this work
2095 2056 2037 2013 this work
2088 2046 2027 2010 this work
ref
2a
2b
2c
2d
2e
2f
Et
t-Bu
6
PhCH2
allyl
6
Ph
C6F5
NC6H11,
18 (1,2-η)-SCNMe2,19 (1,3-η)-S2CCo3(CO)8,20 (1,3-
η)-SC(R)NH (R ) Me, Ph, p-MeOPh),21 (1,3-η)-S2COMe,22
η-PPh2,23 (1,2-η)-SPMe2,24 and (1,2,3-η)-(PMe2)2Co-
(CO)2.24 Earlier experiments to prepare at least some
of these complexes by starting from 1 failed.25
All the above-mentioned complexes containing the
Co3(CO)7(µ-X)(µ3-S) framework proved to be rather
stable, and this suggests that a large number of more
such compounds may exist. The lack of a rational way
to synthesize these clusters, however, prevented a
systematic exploration of this field of cobalt carbonyl
cluster chemistry. In this paper we now report about a
simple reaction which allows the transformation of
paramagnetic 1 into its diamagnetic substituted deriva-
tives Co3(CO)7(µ-X)(µ3-S).
2g
2h
2-naphthyl
HOCH2CH2 2086 2048 2026 2011 this work
on this thiol and (t-BuS)2. When 1 was reacted in
hexane solution under Ar with a small excess of t-BuSH
or (t-BuS)2, the starting complex was completely trans-
formed within a few hours and the IR spectra of both
solutions showed the bands characteristic of the desired
complex. The compound formed was, however, found
to be an oil, and therefore it was transformed by excess
PPh3 into a substituted derivative which was character-
ized by X-ray crystallography (vide infra) as Co3(CO)4-
(PPh3)3(µ-SBut)(µ3-S) (3).
This result suggested that the correct formulation of
the Co3(CO)6(µ3-SR)(µ3-S) complexes is Co3(CO)7(µ-SR)-
(µ3-S) (2) and that they are formed according to reactions
1 or 2 from 1.
Resu lts a n d Discu ssion
The evolution of H2 in reaction 1 could be proven by
GLC.
Syn th esis of Co3(CO)7(µ-X)(µ3-S) Com p lexes. The
reaction of 1 with thiols and disulfides, which according
to an earlier report6 yields “Co3(CO)6(µ3-SR)(µ3-S)” type
complexes (R ) Et, CH2Ph), was chosen as a starting
point to find a broadly applicable reaction for the
synthesis of substituted derivatives of Co3(CO)9(µ3-S).
The first object of our work was to prepare a sufficiently
stable representative of the Co3(CO)6(µ3-SR)(µ3-S) type
complexes in order to determine its structure unequivo-
cally by X-ray crystallography.
Co (CO) (µ -S)
+ RSH f
3
9
3
1
1
Co (CO) (µ-SR)(µ -S)
+ 2CO + /2H2 (1)
3
7
3
2
1
Co (CO) (µ -S)
+ /2(RS)2 f
3
9
3
1
Co (CO) (µ-SR)(µ -S)
+ 2CO (2)
When 1 was reacted in hexane solution with several
different thiols which do not contain other functional
groups capable of interacting with cobalt carbonyls, it
was found that all of these yield as main products
carbonyl complexes having very similar IR spectra in
the νCO region and belong therefore to the same class
of compounds. These spectra were completely analo-
gous to those of the previously described Co3(CO)6(µ3-
SR)(µ3-S) (R ) Et, PhCH2) derivatives. Table 1 compiles
the IR spectroscopic data of the main products present
in the hexane solutions obtained in these reactions.
Among the thiols tested, t-BuSH gave the cleanest
reaction, and further efforts were concentrated therefore
3
7
3
2
The evidence for the formation of a complex contain-
ing the Co3(CO)7(µ-X)(µ3-S) framework from Co3(CO)9-
(µ3-S) in a stoichiometrically clean substitution reaction
was, however, still not unequivocal. One might argue
that the primary product of the reaction between Co3-
(CO)9(µ3-S) and RSH was Co3(CO)6(µ3-SR)(µ3-S) and the
µ3-SR ligand was only later transformed into the
µ-SR ligand by triphenylphosphine during the formation
of 3.
To prove the formation of Co3(CO)7(µ-X)(µ3-S) type
complexes from Co3(CO)9(µ3-S) by reactions such as (1)
and (2), a more direct evidence had to be found. When
1 was reacted with bis(methylthio(thiocarbonyl)) disul-
fide, (MeSCS2)2, the expected Co3(CO)7(µ-1,3-η)-S2CSMe)-
(µ3-S) (4) could be obtained in crystalline form and was
characterized by X-ray crystallography (vide infra). The
formation of 4 from 1 is described by reaction 3.
(16) Wei, C. H. Inorg. Chem. 1984, 23, 2973.
(17) Stanghellini, P. L.; Gervasio, G.; Rossetti, R.; Bor, G. J .
Organomet. Chem. 1980, 187, C37.
(18) Patin, H.; Mignani, G.; Mahe´, C.; Le Marouille, J .-Y.; Benoit,
A.; Grandjean, D.; Levesque, G. J . Organomet. Chem. 1981, 208, C39.
(19) Mahe´, C.; Patin, H.; Benoit, A.; Le Marouille, J .-Y. J . Orga-
nomet. Chem. 1981, 216, C15.
(20) Gervasio, G.; Rossetti, R.; Stanghellini, P. L.; Bor, G. Inorg.
Chem. 1982, 21, 3781.
1 + 1/2(ΜeSCS2)2 f 4 + 2CO
(3)
(21) Benoit, A.; Darchen, A.; Le Marouille, J .-Y.; Mahe´, C.; Patin,
H. Organometallics 1983, 2, 555.
(22) Marko´, L.; Gervasio, G.; Stanghellini, P. L.; Bor, G. Transition
Met. Chem. 1985, 10, 344.
(23) Edwards, A. J .; Martin, A.; Mays, M. J .; Nazar, D.; Raithby, P.
R.; Solan, G. A. J . Chem. Soc., Dalton Trans. 1993, 355.
(24) Gervasio, G.; Musso, F.; Vastag, S.; Bor, G.; Szalontai, G.;
Marko´, L. J . Cluster Sci. 1994, 5, 401.
(25) Bor, G.; Gervasio, G.; Rossetti, R.; Stanghellini, P. L. 29th
IUPAC Congress, Cologne, Germany, J une 5-10, 1983; Abstract of
Papers, Poster No. 60.
Reactions 1-3 suggest that the reaction of 1 with
compounds containing a S-H or a S-S bond (see also
the reaction with S85) may be quite general. To further
support this assumption, 1 was reacted with dithiocar-
bonic acid methyl ester, MeOCS2H (liberated in situ
from MeOCS2K by acetic acid), and dithiobenzoic acid,

4220 Organometallics, Vol. 17, No. 19, 1998
Vastag et al.
PhCS2H. In both cases the expected Co3(CO)7(µ-X)(µ3-
S) type complexes, Co3(CO)7(µ-(1,3-η)-S2COMe)(µ3-S)22
(5) and Co3(CO)7(µ-(1,3-η)-S2CPh)(µ3-S) (6), respectively,
were the only metal carbonyl derivatives formed as
shown by the IR spectra of the reaction mixtures (eqs 4
and 5).
1 + MeOCS2H f 5 + 2CO + 1/2
1 + PhCS2H f 6 +2CO +1/2
(4)
(5)
Complexes 5 and 6 could be isolated in solid form.
Complex 5 has been already described by us earlier22
and was identified by the identity of its IR spectrum
between 400 and 2000 cm-1 with the published one. As
expected, the yield obtained in reaction 5 (17%) was
better than that obtained by the previous method
starting from CoCl2‚6H2O (11%, based on Co)22 and the
isolation of 5 did not require chromatographic purifica-
tion. The structure of 6 was determined by X-ray
crystallography (vide infra). The molecular hydrogen
evolved in these reactions was detected by GLC.
The successful reactions with compounds containing
an SH group prompted us to investigate the possibility
of an analogous reaction with compounds containing a
P-H bond. In this way we hoped to synthesize Co3-
(CO)7(µ-X)(µ3-S) type complexes having a phosphorus
atom as donor in the bridging ligand X, as in the already
known Co3(CO)7(µ-PPh2)(µ3-S)23 and Co3(CO)7(µ-1,2-
(2-SPMe2)(µ3-S).24
F igu r e 1. ORTEP plot of Co3(CO)4(PPh3)3(µ-S-t-Bu)(µ3-S)
(3), with atom-labeling scheme.
the reaction rates were found to be poorly reproducible
and the only unambiguous conclusion was that the
reaction is strongly inhibited by CO.
P r ep a r a tion of 1. Three methods have been de-
scribed for the preparation of 1: from Co2(CO)8 and
elemental sulfur (yield 12%),1a from HCo(CO)4 and Na2-
SO3 (yield 18%),5a and from Co2(CO)8 and PhSH (yield
30%).27 We have now found that 1 can be conveniently
prepared in over 60% yield from Co2(CO)8 and ethylene
sulfide under CO in hexane solution at room tempera-
ture. Ethylene is evolved in the reaction (eq 8).
In fact, when 1 was reacted with HPPh2 and HP(S)-
Ph2, the complexes Co3(CO)7(µ-PPh2)(µ3-S) (7) and Co3-
(CO)7(µ-(1,2-η)-SPPh2)(µ3-S) (8), respectively, could be
obtained in clean reactions. The identity of 7 obtained
in this way with that obtained from Co2(CO)8 and
Co2(CO)8 + C2H4S f 1 + C2H4
(8)
23
This desulfurization reaction seems to be quite gen-
eral. In a qualitative experiment the reaction between
2-phenylthiirane and Co2(CO)8 was tested and 1 and
styrene were identified as the only products. The
observation that Co2(CO)8 is inert against 2-phenylthi-
irane at room temperature under 27 bar of CO pres-
sure28 suggests that carbon monoxide strongly inhibits
the reaction.
PhSPPh2 was shown by its IR and NMR spectrum;
the structure of the new complex 8 was determined by
X-ray crystallography (vide infra) and found to be
similar to that of the dimethyl analogue.24 Hydrogen
was detected in the gases evolved by GLC. Accordingly,
the stoichiometries of these reactions (eqs 6 and 7) are
like those observed with compounds having S-H bonds
that have been discussed above (eqs 4 and 5).
It should be further mentioned that thiiranes and
alkyl halides can be carbonylated to â-mercapto acids
with Co2(CO)8 as catalyst in the presence of bases under
phase transfer conditions.29 Due to the very diffferent
reaction conditions, however, it is not probable that 1
plays any role in this latter reaction.
1 + HPPh f 7 + 2CO + 1/ H2
(6)
(7)
2
2
1 + HP(S)Ph f 8 + 2CO + 1/ H2
2
2
The analogy between sulfur and phosphorus com-
pounds in their reactivity against 1 was found to be in-
complete. In contrast to compounds with S-S bonds,
those having P-P bonds did not react under the
conditions used in our experiments.
Reactions 1-7 may be regarded as specific examples
of a general reaction of 1 which eliminates the surplus
electron of the paramagnetic cluster and transforms it
into an electron-precise derivative by substituting two
CO ligands with a three-electron-donor ligand. Since
in this process the average oxidation state of the three
cobalt atoms is increased from +0.33 to +1, it may be
called an “oxidative substitution”.
Episulfides have been already used for the prepara-
tion of Fe3(CO)9(µ3-S)2 from Fe3(CO)12.30
Cr ysta l Str u ctu r es of Com p lexes 3, 4, 6, a n d 8.
Figures 1-4 show the molecules of the complexes Co3-
(CO)4(PPh3)3(µ-S-t-Bu)(µ3-S) (3), Co3(CO)7(µ-(1,3-η)-S2-
CSMe)(µ3-S) (4), Co3(CO)7(µ-(1,3-η)-S2CPh)(µ3-S) (6), and
Co3(CO)7(µ-(1,2-η)-SPPh2)(µ3-S) (8), respectively. The
most relevant distances and angles are listed in Tables
2-5.
The four complexes have a common Co3S core with a
ligand bridging a Co-Co edge and forming three-
(26) Wei, C. H.; Dahl, L. F. Cryst. Struct. Commun. 1975, 4, 583.
(27) Klumpp, E.; Bor, G.; Marko´, L. Chem. Ber. 1967, 100, 1451.
(28) Calet, S.; Alper, H. Tetrahedron Lett. 1986, 27, 3573.
(29) Calet, S.; Alper, H. Organometallics 1987, 6, 1625.
(30) King, R. B. Inorg. Chem. 1963, 2, 326.
The mechanism of these reactions is unclear at
present. Experiments to determine the kinetics of the
reaction with t-BuSH and (t-BuS)2 were not successful:

Rational Synthesis of Co3(CO)7(µ-X)(µ3-S) Complexes
Organometallics, Vol. 17, No. 19, 1998 4221
Ta ble 2. Selected Bon d Len gth s (Å) a n d Bon d
An gles (d eg) for 3
Co(1)-Co(2)
Co(1)-Co(3)
Co(1)-S(1)
Co(1)-S(2)
Co(1)-P(1)
Co(1)-C(11)
Co(2)-Co(3)
Co(2)-S(1)
Co(2)-S(2)
Co(2)-P(2)
Co(2)-C(21)
Co(2)-C(32)
Co(3)-S(1)
2.495(1)
2.603(1)
2.183(2)
2.254(2)
2.214(2)
1.745(6)
2.565(1)
2.241(2)
2.280(2)
2.257(2)
1.769(5)
2.285(6)
2.151(2)
Co(3)-P(3)
Co(3)-C(31)
Co(3)-C(32)
S(2)-C(1)
2.202(2)
1.746(6)
1.779(7)
1.863(5)
1.830(5)
1.509(8)
1.520(8)
1.498(9)
1.156(7)
1.145(7)
1.153(8)
1.164(8)
P-Cav
C(1)-C(2)
C(1)-C(3)
C(1)-C(4)
C(11)-O(11)
C(21)-O(21)
C(31)-O(31)
C(32)-O(32)
Co(2)-Co(1)-Co(3)
Co(2)-Co(1)-S(2)
Co(3)-Co(1)-S(2)
S(1)-Co(1)-S(2)
S(2)-Co(1)-P(1)
S(2)-Co(1)-C(11)
Co(1)-Co(2)-Co(3)
Co(1)-Co(2)-S(2)
Co(3)-Co(2)-S(2)
S(1)-Co(2)-S(2)
S(2)-Co(2)-P(2)
S(2)-Co(2)-C(21)
Co(3)-Co(2)-C(32)
60.4(1)
57.1(1)
116.6(1)
84.5(1)
107.4(1)
109.5(2)
61.9(1)
56.1(1)
117.1(1)
82.5(1)
105.4(1)
97.7(2)
42.6(2)
S(2)-Co(2)-C(32)
Co(1)-Co(3)-Co(2)
Co(2)-Co(3)-C(32)
Co(1)-S(2)-Co(2)
Co(1)-S(2)-C(1)
Co(2)-S(2)-C(1)
Co-P-Cav
Co(1)-C(11)-O(11)
Co(2)-C(21)-O(21)
Co(3)-C(31)-O(31)
Co(2)-C(32)-Co(3)
Co(2)-C(32)-O(32)
Co(3)-C(32)-O(32)
153.3(2)
57.7(1)
60.3(2)
66.8(1)
120.2(2)
120.1(2)
115.8(2)
177.4(5)
175.0(5)
177.2(5)
77.2(2)
F igu r e 2. ORTEP plot of Co3(CO)7(µ-(1,3-η)-S2CSMe)(µ3-
S) (4), with atom-labeling scheme.
128.8(5)
153.8(5)
Ta ble 3. Selected Bon d Len gth s (Å) a n d Bon d
An gles (d eg) for 4
Co(1)-Co(2)
Co(1)-Co(3)
Co(1)-S(1)
Co(1)-S(3)
Co(1)-C(11)
Co(1)-C(13)
Co(2)-Co(3)
Co(2)-S(2)
Co(2)-S(3)
Co(2)-C(21)
Co(2)-C(23)
Co(3)-S(3)
Co(3)-C(31)
2.486(2)
2.524(2)
2.258(3)
2.154(3)
1.815(11)
1.824(11)
2.510(2)
2.248(3)
2.152(3)
1.812(10)
1.830(10)
2.173(2)
1.773(12)
Co(3)-C(32)
Co(3)-C(33)
S(1)-C(1)
1.819(9)
1.826(11)
1.685(9)
1.680(8)
1.748(9)
1.774(11)
1.134(14)
1.089(14)
1.122(14)
1.110(13)
1.138(17)
1.139(12)
1.101(14)
S(2)-C(1)
S(4)-C(1)
S(4)-C(2)
C(11)-O(11)
C(13)-O(13)
C(21)-O(21)
C(23)-O(23)
C(31)-O(31)
C(32)-O(32)
C(33)-O(33)
F igu r e 3. ORTEP plot of Co3(CO)7(µ-(1,3-η)-S2CPh)(µ3-S)
(6), with atom-labeling scheme.
Co(2)-Co(1)-Co(3)
Co(2)-Co(1)-S(1)
Co(1)-Co(2)-Co(3)
Co(1)-Co(2)-S(2)
Co(1)-Co(3)-Co(2)
Co(1)-S(1)-C(1)
Co(2)-S(2)-C(1)
Co(1)-S(3)-Co(2)
Co(1)-S(3)-Co(3)
Co(2)-S(3)-Co(3)
C(1)-S(4)-C(2)
60.1(1) S(1)-C(1)-S(2)
96.2(1) S(1)-C(1)-S(4)
60.7(1) S(2)-C(1)-S(4)
127.7(5)
112.6(5)
119.7(5)
97.4(1) Co(1)-C(11)-O(11) 177.3(11)
59.2(1) Co(1)-C(13)-O(13) 179.1(9)
109.6(3) Co(2)-C(21)-O(21) 175.1(11)
109.1(3) Co(2)-C(23)-O(23) 179.2(10)
70.5(1) Co(3)-C(31)-O(31) 178.0(10)
71.4(1) Co(3)-C(32)-O(32) 179.1(9)
70.9(1) Co(3)-C(33)-O(33) 177.8(9)
104.9
if two Co-Co bonds are bridged by ligands (S-t-Bu and
asymmetric CO) and thus a shortening on these bonds
is acting. The behavior of complex 3 may be attributed
either to the steric hindrance or to the electronic effect
of the three PPh3 ligands; in fact, the PPh3 ligand is a
better σ-donor and a worse π-acceptor than CO and
therefore the substitution has a swelling effect on the
cluster. The same effect is detectable in the bisubsti-
tuted complex Co3(CO)5(PPh3)2(µ3-S)(SPMe2)24 (average
Co-Co ) 2.540(9) Å and average Co-Sap ) 2.172(8) Å)
and in the monosubstituted Co3(CO)6(PPh3)(µ3-S)(S2-
COSMe) (average Co-Co ) 2.520(1) Å and average Co-
Sap ) 2.160(1) Å).20
F igu r e 4. ORTEP plot of Co3(CO)7(µ-(1,2-η)-SPPh2)(µ3-S)
(8), with atom-labeling scheme.
(complex 3), four- (complex 8), or five-membered (com-
plexes 4 and 6) equatorial rings. The structural features
of these 48-electron cores are summarized in Table 6
and compared with the core of Co3(CO)9(µ3-S) (49
electrons).
As expected, Co3(CO)9(µ3-S) has the biggest cluster;
among the other complexes, however, complex 3 shows
the greatest average Co-Co and Co-Sap distances, even
The data of Table 6 show that the least influenced
parameter is the Co-S distance as compared to the
angle around Sap and to the distance of Sap from the Co3
plane. Furthermore, the Co-Co bond bridged by the

4222 Organometallics, Vol. 17, No. 19, 1998
Vastag et al.
Ta ble 4. Selected Bon d Len gth s (Å) a n d Bon d An gles (d eg) for 6
molecule
molecule
A
B
A
B
Co(1)-Co(2)
Co(1)-Co(3)
Co(1)-S(1)
Co(1)-S(3)
Co(1)-C(11)
Co(1)-C(13)
Co(2)-Co(3)
Co(2)-S(2)
Co(2)-S(3)
Co(2)-C(21)
Co(2)-C(23)
Co(3)-S(3)
Co(3)-C(31)
Co(3)-C(32)
Co(3)-C(33)
S(1)-C(1)
2.475(1)
2.543(1)
2.248(1)
2.151(1)
1.814(4)
1.806(4)
2.523(1)
2.238(1)
2.148(1)
1.794(4)
1.808(5)
2.164(1)
1.823(4)
1.812(5)
1.814(4)
1.681(4)
2.472(1)
2.512(1)
2.234(1)
2.152(1)
1.812(4)
1.806(4)
2.527(1)
2.248(1)
2.158(1)
1.813(5)
1.791(4)
2.176(1)
1.814(4)
1.812(5)
1.801(5)
1.686(3)
S(2)-C(1)
1.686(4)
1.488(5)
1.397(6)
1.390(6)
1.382(7)
1.361(9)
1.382(8)
1.380(7)
1.123(6)
1.117(5)
1.132(5)
1.126(6)
1.124(5)
1.130(6)
1.120(5)
1.672(4)
1.490(6)
1.385(6)
1.388(6)
1.384(8)
1.368(8)
1.364(8)
1.399(8)
1.132(5)
1.126(5)
1.123(6)
1.141(5)
1.136(5)
1.131(7)
1.142(6)
C(1)-C(2)
C(2)-C(3)
C(2)-C(7)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
C(6)-C(7)
C(11)-O(11)
C(13)-O(13)
C(21)-O(21)
C(23)-O(23)
C(31)-O(31)
C(32)-O(32)
C(33)-O(33)
molecule
molecule
A
B
A
B
Co(2)-Co(1)-Co(3)
Co(2)-Co(1)-S(1)
S(1)-Co(1)-C(11)
S(1)-Co(1)-C(13)
Co(1)-Co(2)-Co(3)
Co(1)-Co(2)-S(2)
S(2)-Co(2)-C(21)
S(2)-Co(2)-C(23)
Co(1)-Co(3)-Co(2)
Co(1)-S(1)-C(1)
Co(2)-S(2)-C(1)
60.4(1)
60.9(1)
96.9(1)
95.1(1)
96.1(1)
60.3(1)
96.5(1)
97.0(2)
94.0(2)
58.7(1)
110.2(2)
110.2(1)
S(1)-C(1)-S(2)
125.2(2)
126.2(3)
115.6(3)
118.2(3)
177.8(4)
179.0(4)
177.5(4)
178.7(4)
177.6(4)
179.7(4)
178.5(4)
95.2(1)
97.5(1)
93.0(1)
61.2(1)
97.5(1)
95.5(1)
96.3(2)
58.5(1)
111.4(1)
109.7(1)
S(1)-C(1)-C(2)
117.2(3)
117.6(3)
177.2(4)
178.0(4)
178.4(4)
178.3(5)
178.8(4)
178.8(4)
177.8(4)
S(2)-C(1)-C(2)
Co(1)-C(11)-O(11)
Co(1)-C(13)-O(13)
Co(2)-C(21)-O(21)
Co(2)-C(23)-O(23)
Co(3)-C(31)-O(31)
Co(3)-C(32)-O(32)
Co(3)-C(33)-O(33)
Ta ble 5. Selected Bon d Len gth s (Å) a n d Bon d
An gles (d eg) for 8
complexes 4, 6, and 8 with one axial CO on each cobalt
atom and one (on Co(1) and Co(2)) or two equatorial
CO’s (on Co(3)). Complex 3, however, shows a quite
different scheme, owing to the great bulk of the PPh3
ligand on Co(3) that pushes away an equatorial CO.
This ligand thus becomes an asymmetrical bridge below
the Co3 plane halfway between an equatorial and an
axial CO.
Co(1)-Co(2)
Co(1)-Co(3)
Co(1)-S(1)
Co(1)-S(2)
Co(1)-C(11)
Co(1)-C(13)
Co(2)-Co(3)
Co(2)-P(1)
Co(2)-S(1)
Co(2)-C(21)
Co(2)-C(23)
Co(3)-S(1)
2.470(1)
2.533(1)
2.155(1)
2.312(1)
1.797(3)
1.798(3)
2.522(1)
2.205(1)
2.157(1)
1.806(3)
1.786(2)
2.167(1)
Co(3)-C(31)
Co(3)-C(32)
Co(3)-C(33)
P(1)-S(2)
C(11)-O(11)
C(13)-O(13)
C(21)-O(21)
C(23)-O(23)
C(31)-O(31)
C(32)-O(32)
C(33)-O(33)
1.820(3)
1.811(3)
1.805(3)
2.033(1)
1.126(4)
1.124(4)
1.120(4)
1.133(3)
1.129(4)
1.131(3)
1.127(3)
In complex 3 S(2) is an asymmetrical bridge with the
longest C(2)-S(2) bond nearly trans (153°) to CO(32)
and with the t-Bu group below the Co(1)Co(2)S(2) plane
(anti with respect to Sap). In complexes 4 and 6 the five-
membered rings are roughly planar, including S(4) and
C(2) for complex 4 (mean deviation 0.04 Å) and atom
C(2) for complex 6 (mean deviation 0.06 and 0.02 Å);
this planarity is in keeping with a π delocalization over
the entire ligand with a more pronounced double-bond
character on the C(1)-S(1) and C(1)-S(2) bonds (1.68
Å average).31 The phenyl ring in complex 6 is not
coplanar with the five-membered ring and forms angles
of 20 and 38° for molecules A and B, respectively,
showing the mobility of this part of the molecule (in the
monoclinic form this angle is 56°). In complex 8 the
four-membered ring has a mean deviation of 0.04 Å, the
coordination around P is tetrahedral, and the P-S
distance (2.033(1) Å) corresponds to an elongated double
bond. The Co(1)-S(2) bond (2.312(1) Å) is longer than
all the other Co-S distances of the other complexes.
Co(2)-Co(1)-Co(3)
Co(2)-Co(1)-S(2)
S(2)-Co(1)-C(11)
S(2)-Co(1)-C(13)
Co(1)-Co(2)-Co(3)
Co(1)-Co(2)-P(1)
P(1)-Co(2)-C(21)
P(1)-Co(2)-C(23)
Co(1)-Co(3)-Co(2)
60.5(1)
88.0(1)
98.0(1)
95.8(1)
61.0(1)
80.5(1)
102.0(1)
97.8(1)
58.5(1)
Co(2)-P(1)-S(2)
103.2(1)
88.0(1)
Co(1)-S(2)-P(1)
Co(1)-C(11)-O(11)
Co(1)-C(13)-O(13)
Co(2)-C(21)-O(21)
Co(2)-C(23)-O(23)
Co(3)-C(31)-O(31)
Co(3)-C(32)-O(32)
Co(3)-C(33)-O(33)
177.9(3)
178.2(3)
177.4(3)
179.5(2)
177.3(3)
177.0(2)
177.7(2)
organic ligand is always shorter than the other two Co-
Co bonds. The influences, however, of the three-, four-
or five-membered rings on the Co3S core are not
systematic because the differences are of the same order
of magnitude as the differences between two identical
molecules in the same asymmetric unit (complex 6).
The organic ligands substitute two equatorial CO’s,
forming roughly planar rings slightly tilted toward Sap
(the dihedral angles with the Co3 plane are 11° (complex
3), 16° (complexes 4 and 6), and 10° (complex 8)); in Co3-
(CO)9(µ3-S) the tilting angle of the COeq’s is 25°. The
situation of the CO ligands is nearly the same for
Exp er im en ta l Section
Gen er a l Meth od s. All manipulations with air-sensitive
compounds were carried out by the standard Schlenk tech-
niques using deoxygenated, dry solvents and gases. Infrared
spectra were recorded on
a Specord IR 75 (Carl Zeiss,
(31) Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen,
A. G. J . Chem. Soc., Perkin Trans. 2 1987, S1.
Germany) spectrometer and were calibrated with benzene

Rational Synthesis of Co3(CO)7(µ-X)(µ3-S) Complexes
Organometallics, Vol. 17, No. 19, 1998 4223
Ta ble 6. Selected Geom etr ic P a r a m eter s of th e Co3S Cor e in Rela ted Com p lexes
6
distances and angles
Co3(CO)9S
2.637(7)
3
4
8
Co(1)-Co(2), Å
Co(1)-Co(3), Å
Co(2)-Co(3), Å
Co-Coav , Å
2.495(1)
2.603(1)
2.565(1)
2.554(1)
2.183(2)
2.241(2)
2.151(2)
2.192(2)
1.62
2.486(2)
2.524(2)
2.510(2)
2.507(2)
2.154(3)
2.152(3)
2.173(2)
2.160(3)
1.60
2.475(1)
2.543(1)
2.523(1)
2.514(1)
2.151(1)
2.148(1)
2.164(1)
2.154(1)
1.59
2.472(1)
2.512(1)
2.527(1)
2.504(1)
2.152(1)
2.158(1)
2.176(1)
2.162(1)
1.61
2.470(1)
2.533(1)
2.522(1)
2.508(1)
2.155(1)
2.157(1)
2.167(1)
2.160(1)
1.60
Co(1)-Sap, Å
Co(2)-Sap, Å
Co(3)-Sap, Å
Co-Sav, Å
2.14(1)
1.50
76.1(3)
Co3‚‚‚Sap average
Co-Sap-Co average
71.3(2)
70.9(1)
71.4(1)
70.8(1)
71.0(1)
(1959.6 cm-1). 31P NMR spectra were obtained on a Varian
Unity 300 spectrometer; the spectra were referenced to 85%
H3PO4. Gas chromatographic analyses were carried out on
an HP 5890 chromatograph equipped with a Chrompack 5 Å
Molsieve column and a TCD detector (for H2) or with a
Paraplot Q column and an FID detector (for C2H4).
Ma ter ia ls. Ethylene sulfide, and the thiols EtSH, PhCH2-
SH, t-BuSH, CH2dCHCH2SH, HOCH2CH2SH, C6H11SH, PhSH,
and 2-C10H7SH, and (t-BuS)2 were commercial products (Al-
drich); Co2(CO)8,32 Ph2PH,33 Ph2P(S)H,34 PhCS2H,35 (MeCS2)2,36
and MeOCS2K37 were prepared according to literature meth-
ods.
3: Co, 14.77 (14.9); S, 5.36 (5.2); P, 7.76 (7.7). IR (in Nujol):
1
1981 vs, 1948 s, 1915 m, 1815 w,br cm -1. H NMR (CD2Cl2):
δ 1.26 (s, Me), 7.25-7.48 (m, Ph). 31P NMR (CD2Cl2): δ 37.2
(∆ν ) 460 Hz) ppm. 13C NMR (CD2Cl2) δ 32.8 (s, Me), 43.6 (s,
CMe3), 214 (CO) ppm; the signals of the phenyl carbon atoms
show the presence of two types of PPh3 ligands with an
intensity ratio of about 1:2 at 128.2 (d, 1J PC ) 8.8 Hz, C3), 129.8
1
1
(s, C4), 133.7 (d, J PC ) 11.5 Hz, C2), 136.3 (d, J PC ) 37 Hz,
C
ipso) ppm, and 128.4 (d, 1J PC ) 10.4 Hz, C3), 129.6 (s, C4), 134.3
(d, J PC ) 9.6 Hz, C2), 136.8 (d, J PC ) 37 Hz, Cipso) ppm; the
two sets of signals are assigned to the PPh3 ligand on Co(3)
and the two PPh3 ligands on Co(1) and Co(2), respectively.
1
1
P r ep a r a tion of Co3(CO)9(µ3-S) (1). To 1.71 g (5 mmol)
of Co2(CO)8 dissolved under CO in 40 mL of hexane was added
210 mg (208 µL, 3.5 mmol) of ethylene sulfide and the solution
stirred until the IR spectra of samples taken from the reaction
mixture indicated that all Co2(CO)8 has been consumed (about
4 h). The dark brown solution was filtered and the filtrate
first kept at 2-4 °C for 1 day and then at -18 °C for 3 days.
The black crystals were filtered off and dried under vacuum.
Yield: 0.96 g (2.08 mmol), 62.5% based on Co. According to
Syn th esis of Co3(CO)7(µ-(1,3-η)-S2CSMe)(µ3-S) (4).
A
230 mg (0.50 mmol) amount of 1 and 56.5 mg (0.25 mmol) of
bis(methylthio(thiocarbonyl)) disulfide, (MeSCS2)2, were dis-
solved in 20 mL of CH2Cl2, and the mixture was stirred under
Ar for 3 h. The reaction mixture was evaporated to dryness,
dissolved in 15 mL of hexane, and filtered. The IR spectrum
of the clear solution showed only the presence of 4. The solu-
tion was stored at 2-4 °C for 1 week. The resulting crystals
were recrystallized from hexane. Yield: 51 mg (0.098 mmol)
of black cubes, 19.6%. Anal. Calcd (found) for 4: Co, 33.47
its IR spectrum in hexane the product is contaminated by
5a,26
small amounts (2-3%, estimated) of Co4(CO)10S2
formed
(33.1); S, 24.28 (24.6). IR (in hexane): 2093 s, 2056 vs, 2051
-1
s, 2033 m cm
.
1H NMR (CD2Cl2): δ 2.66s ppm. 13C NMR
as a byproduct. This latter complex is generally rather inert
and does not interfere with the reactions described in this
paper. Attempts to further purify 1 by recrystallization
resulted in a more contaminated product because the tetra-
nuclear complex is the less soluble one. On chromatography
on a silica gel column complex 1 decomposes.
Rea ction of 1 w ith Th iols a n d Disu lfid es (Gen er a l
P r oced u r e for th e P r ep a r a tion of Com p lexes 2). A 20-
25 mg (∼0.5 mmol) amount of 1 and about 0.6 mmol of the
thiol or 0.3 mmol of the disulfide were dissolved in 5 mL of
CH2Cl2 under Ar and stirred until the reaction was complete
(IR monitoring, 2-4 h, depending on the organic reactant).
The reaction mixture was then evaporated to dryness in vacuo
and dissolved in hexane. The IR data of the hexane solutions
obtained are compiled in Table 1.
Syn th esis of Co3(CO)4(P P h 3)3(µ-S-t-Bu )(µ3-S) (3). To
200 mg (0.435 mmol) of 1 dissolved under Ar in 20 mL of
hexane were added 40 mg (50 µL, 0.446 mmol) of t-BuSH and
the reaction mixture was stirred. After the transformation of
1 into 3 was complete (IR monitoring, usually the next day),
690 mg (2.63 mmol) of PPh3 dissolved in 15 mL of hexane was
added and the reaction mixture stored at room temperature
for 2 days. The precipitate formed was filtered off and
recrystallized from 2 mL of CH2Cl2/20 mL of hexane using the
slow diffusion method. Yield after 3 days: 210 mg (0.175
mmol) of shiny black crystals, 60%. Anal. Calcd (found) for
(CD2Cl2): δ 22.8 (s, Me), 196 (broad, CO), 247.8 (s, SCS2) ppm.
Syn th esis of Co3(CO)7(µ-(1,3-η)-S2COMe)(µ3-S) (5).
A
184.4 mg (0.40 mmol) amount of 1 and 64.5 mg (0.44 mmol)
of MeOCS2K were dissolved under Ar in 20 mL of CH2Cl2, and
25.1 µL (0.44 mmol) of glacial acetic acid was slowly added to
the solution with constant stirring. After 2 h the reaction
mixture was evaporated to dryness and dissolved in 3 mL of
hexane and the hexane solution cooled to -40 °C. Yield: 38.3
mg (0.075 mmol) of shiny black clumps, 17%. 1H NMR (CD2-
Cl2): δ 4.04 s ppm. 13C NMR (CD2Cl2): δ 67.2 (s, Me), 190-
210 (very broad, CO), 236.1 (s, OCOMe) ppm.
Syn th esis of Co3(CO)7(µ-(1,3-η)-S2CP h )(µ3-S) (6). A 170
mg (0.37 mmol) amount of 1 and 63 µL (0.41 mmol) of PhCS2H
were dissolved under Ar in 20 mL of CH2Cl2, and the mixture
was stirred for 2 h. The reaction mixture was then evaporated
to dryness and dissolved in 3 mL of hexane and the hexane
solution cooled to -40 °C. Yield: 68 mg (0.12 mmol) of black
powder, 33%. Anal. Calcd (found) for 6: Co, 31.67 (31.3); S,
17.23 (17.4). IR (in hexane): 2092 s, 2055 vs, 2050 s, 2033 m,
2015 vw cm-1 13C NMR (CD2Cl2): δ 196 (broad, CO), 250.0
.
(s, S2CPh); the signals of the phenyl carbon atoms are at 126.1
(C2), 128.5 (C3), 132.2 (C4), 148.7 (Cipso) ppm. Crystals suitable
for X-ray determination were obtained by cooling a toluene
solution of the complex.
Syn th esis of Co3(CO)7(µ-P P h 2)(µ3-S) (7). To 184 mg (0.40
mmol) of 1 dissolved under Ar in 15 mL of hexane was added
80 mg (75 µL, 0.43 mmol) of Ph2PH and the reaction monitored
by IR spectroscopy as described for the preparation of 1. After
the transformation of 1 into 7 was complete (6-8 h), the
reaction mixture was separated by chromatography on a silica
gel column. Using a hexane/CH2Cl2 (4/1) solvent mixture as
eluent gave 7 as the first fraction which was evaporated to
dryness under vacuum, dissolved in 5 mL of hexane, and cooled
(32) Szabo´, P.; Marko´, L.; Bor, G. Chem. Technol. (Berlin) 1961, 13,
549.
(33) Gree, W.; Shaw, R. A.; Smith, B. C. Inorg. Synth. 1976, 9, 19.
(34) Peters, G. J . Am. Chem. Soc. 1960, 82, 4751.
(35) Bost, W.; Otis, A.; Shealey, L. J . Am. Chem. Soc. 1951, 73, 25.
(36) (a) Knoth, W.; Gattow, G. Z. Z. Anorg. Allg. Chem., 1987, 554,
172. (b) Gervasio, G.; Vastag, S.; Szalontai, G.; Marko´, L. J . Organomet.
Chem. 1997, 533, 187.
(37) Drawert, F.; Reuther, K.-H.; Born, F. Chem. Ber. 1960, 93, 3056.

Ta ble 7. Cr ysta l Da ta , Da ta Collection , a n d Refin em en t P a r a m eter s for 3, 4, 6, a n d 8
3
4
6
8
empirical formula
fw
C
62H54Co3O4P3S2
C9H3Co3O7S4
528.1
C14H5Co3O7S3
558.2
C19H10Co3O7PS2
622.2
1196.9
crys size, mm; color
cryst syst, space group
unit cell dimens
a, Å
b, Å
c, Å
0.22 × 0.40 × 0.60; brown
0.12 × 0.26 × 0.54; black
0.10 × 0.18 × 0.56; black
0.26 × 0.30 × 0.50; black
monoclinic, P21/n
monoclinic, C2/c
triclinic, P1h
triclinic, P1h
12.952(3)
31.530(4)
14.128(6)
13.755(3)
8.007(2)
30.739(5)
8.178(2)
14.825(3)
16.612(3)
7.755(2)
9.189(2)
16.475(3)
R, deg
82.71(3)
77.01(3)
85.56(3)
1944(1); 4
1.907
2.884
88.40(2)
87.72(2)
86.76(2)
1170.9(4); 2
1.765
â, deg
90.37(2)
91.90(2)
γ, deg
V Å3; Z
5755(3); 4
1.381
1.057
3375(1); 8
2.079
3.435
density (calcd), g/cm3
abs coeff, mm-1
2θ range for data collection, deg
scan type
2.384
2.0-50.0
2.0-55.0
2.0-55.0
2.0-65.0
ω
ω
θ-2θ
θ-2θ
scan speed (variable), deg/min
scan range, deg
no. of rflns collected
no. of indep rflns
no. of obsd rflns
abs cor
max and min transmissn
refinement method
quantity minimized
weighting scheme
no. of params refined
goodness of fita
final R indices (obsd data): R1, wR2a
R indices (all data)
largest and mean ∆/σ
largest diff peak and hole, e/Å3
4.00-20.0
4.00-20.0
4.00-20.0
4.00-20.0
1.60
1.80
3375
2.20
9327
2.00
9157
10 376
9955 (R(int) ) 0.0254)
5845 (F > 4.0σ(F))
semiempirical from ψ scans
0.2119, 0.2616
full-matrix least squares
∑w(Fo - Fc)2
w-1 ) σ2(F) + 0.0002F2
667
2782 (R(int) ) 0.0282)
2114 (F > 4.0σ(F))
semiempirical from ψ scans
0.0884, 1.0000
full-matrix least squares
∑w(Fo - Fc)2
w-1 ) σ2(F) + 0.0020F2
208
8949 (R(int) ) 0.0236)
6494 (F > 4.0σ(F))
semiempirical from ψ scans
0.0132, 0.0454
full-matrix least squares
∑w(Fo - Fc)2
w-1 ) σ2(F) + 0.0015F2
487
8427 (R(int) ) 0.0157)
6049 (F > 4.0σ(F))
semiempirical from ψ scans
0.0683, 0.1160
full-matrix least squares
∑w(Fo - Fc)2
w-1 ) σ2(F) + 0.0012F2
289
1.21
1.38
1.03
0.94
0.0464, 0.0401
0.0974, 0.2933
0.007, 0.001
0.42, -0.39
0.0614, 0.0799
0.0807, 0.1072
0.018, 0.001
0.99, -0.94
0.0382, 0.0504
0.0554, 0.1019
0.034, 0.005
0.55, -0.57
0.0305, 0.0431
0.0491, 0.1820
0.002, 0.000
0.42, -0.25
a
2
2
R1 ) ∑||Fo| - |Fc||/∑|Fo|; wR2 ) [∑[w(Fo - Fc2)2]/∑[w(Fo2)]2]1/2; goodness of fit ) [∑[w(Fo - Fc2)2]/(n - p)]1/2
.

Rational Synthesis of Co3(CO)7(µ-X)(µ3-S) Complexes
to -78 °C. Yield: 98 mg of small black crystals (0.166 mmol),
Organometallics, Vol. 17, No. 19, 1998 4225
tion correction was applied using the method of ref 38. The
structures were solved by direct methods using the Siemens
SHELXTL IRIS package,39 used also for refinement. The non-
hydrogen atoms were anisotropically refined. The last Fourier
difference maps showed peaks corresponding to some H atoms;
the H atoms of the methyls and of the phenyl rings were,
however, calculated and refined riding on the corresponding
carbon atoms with Uiso ) 0.080 Å2. The fractional coordinates
of complexes 3, 4, 6, and 8 are listed in the Supporting
Information.
42%. IR (in hexane): 2077 m, 2034 s, 2015 m (lit.23 IR 2076
-1
m, 2033 s, 2014 m) cm
.
31P NMR (CD2Cl2): δ 213.1 (s, (µ-
PPh2) (lit.23 NMR 71.9 with P(OMe)3 as reference equal to
212.9) ppm.
Syn th esis of Co3(CO)7(µ-(1,2-η)-SP P h 2)(µ3-S) (8). To 184
mg (0.40 mmol) of 1 dissolved under Ar in 15 mL of CH2Cl2
was added 90 mg (0.40 mmol) of Ph2P(S)H and the reaction
monitored by IR spectroscopy as described for the preparation
of 1. After the transformation of 1 into 8 was complete (2-3
h), the reaction mixture was evaporated to dryness in vacuo
and the residue dissolved in 10 mL of hexane. Chromatogra-
phy on silica gel using a hexane/CH2Cl2 (4/1) solvent mixture
as eluent gave 8 as the main fraction. This was concentrated
to 5 mL in vacuo and stored first in a refrigerator and then at
-78 °C. Yield: 107 mg of black crystals (0.172 mmol), 43%.
Anal. Calcd (found) for 8: Co, 28.41 (28.3); S, 10.30 (10.5); P,
4.98 (4.9). IR (in hexane): 2086 s, 2046 vs, 2043 s, 2027 m
.
cm-1 13C NMR (CDCl3): δ 197 (broad, CO), the signals of the
phenyl carbon atoms are at 128.6 and 128.75 (C3), 133.6 and
136.5 (C4), 131.0 and 131.8 (C2), 136.1 and 138.2 (Cipso) ppm.
31P NMR (CDCl3): δ 47 (s, µ-P(S)Ph2) ppm.
X-r a y An a lysis of Com p lexes 3, 4, 6, a n d 8. Crystal data
and parameters of data collections and of refinements are
collected in Table 7. The data were collected at 20 °C on a
Siemens P4 diffractometer graphite-monochromatized with Mo
KR radiation (λ ) 0.710 73 Å). Two standard reflections
measured every 50 reflections showed no decay. The absorp-
Complex 6 crystallizes in two modifications in the triclinic
and monoclinic systems; the data reported in the present work
refer to the triclinic form.
Ack n ow led gm en t. This work was supported by
OTKA grant No. T016260 (Hungary) and the MURST
(Italy).
Su p p or tin g In for m a tion Ava ila ble: Tables giving all
bond angles for 3 and anisotropic thermal parameters for non-
hydrogen atoms, calculated coordinates for H atoms, and
atomic coordination for non-H atoms for 3, 4, 6, and 8 (20
pages). Ordering information is given on any current mast-
head page.
OM980147N
(38) North, A. C. T.; Phillips, D. C.; Mathews, F. S. Acta Crystallogr.
1968, A24, 351.
(39) Sheldrick, G. M. SHELXTL IRIS; Siemens Analytical X-ray
Instruments Inc., Madison, WI, 1990.