Heterotrimetallic iron(II)-nickel(II)-manganese(I) chalcogenolate complexes containing a heteroleptic hexachalcogenolatonickel(II)/homoleptic hexathiolatonickel(II) core

Article abstract of DOI:10.1021/om980833m

Complex cis-[Mn(CO)₄(2-S-C₄H₃S)₂] ^- was employed as a metallo chelating ligand to synthesize [(CO)₄Mn(μ-2-S-C₄H₃S) ₂Ni(μ-2-S-C₄H₃S)₂Mn(CO) ₄] (1) with a square planar Ni^II-thiolate core. The longer Ni^II-Mn^I distances and electronic population of nickel(II) (d⁸) are adopted to rationalize the construction of complex 1. Cleavage of the Mn^I-S bond in complex 1 by an incoming tridentate metallo ligand fac-[Fe(CO)₃(ER)₃]^- (E = S, R = C₄H₃S; E = Se, R = Ph), followed by a thiolate group ([2-S-C₄H₃S]^-) rearranging to bridge two metals, led directly to the anionic [(CO)₃Mn(μ-2-S-C₄H₃S) ₃Ni(μ-ER)₃Fe(CO)₃]^- (E = S, R = C₄H₃S (2); E = Se, R = Ph (3)) with a homoleptic/heteroleptic hexachalcogenolatonickel(II) core, respectively. Dropwise addition of cis-[Mn(CO)₄(2-S-C₄H₃S)₂] to the anionic 2 in THF resulted in formation of a linear trinuclear complex [(CO)₃Mn(μ-2-S-C₄H₃S) ₃Ni(μ-2-S-C₄H₃S)₃Mn-(CO) ₃]^2- (4) possessing a homoleptic hexathiolatonickel(II) core. It seems reasonable to conclude that the d⁶ Mn(I) [(2-S-C₄H₃S)₃Mn(CO)₃]^2- fragment is isolobal with the d⁶ Fe(II) [(ER)₃Fe(CO)₃]^- fragment in complexes 4, 3, and 2.

Full text of DOI:10.1021/om980833m

782
Organometallics 1999, 18, 782-786
Heter otr im eta llic Ir on (II)-Nick el(II)-Ma n ga n ese(I)
Ch a lcogen ola te Com p lexes Con ta in in g a Heter olep tic
Hexa ch a lcogen ola ton ick el(II)/Hom olep tic
Hexa th iola ton ick el(II) Cor e
Wen-Feng Liaw,*,† Chien-Ming Lee,† Lance Horng,§ Gene-Hsiang Lee,‡ and
Shie-Ming Peng‡
Department of Chemistry and Department of Physics, National Changhua University of
Education, Changhua 50058, Taiwan, and Department of Chemistry and Instrumentation
Center, National Taiwan University, Taipei 10764, Taiwan
Received October 5, 1998
Complex cis-[Mn(CO)4(2-S-C4H3S)2]- was employed as a metallo chelating ligand to
synthesize [(CO)4Mn(µ-2-S-C4H3S)2Ni(µ-2-S-C4H3S)2Mn(CO)4] (1) with a square planar NiII-
thiolate core. The longer NiII‚‚‚MnI distances and electronic population of nickel(II) (d8) are
adopted to rationalize the construction of complex 1. Cleavage of the MnI-S bond in complex
1 by an incoming tridentate metallo ligand fac-[Fe(CO)3(ER)3]- (E ) S, R ) C4H3S; E ) Se,
R ) Ph), followed by a thiolate group ([2-S-C4H3S]-) rearranging to bridge two metals, led
directly to the anionic [(CO)3Mn(µ-2-S-C4H3S)3Ni(µ-ER)3Fe(CO)3]- (E ) S, R ) C4H3S (2); E
) Se, R ) Ph (3)) with a homoleptic/heteroleptic hexachalcogenolatonickel(II) core,
respectively. Dropwise addition of cis-[Mn(CO)4(2-S-C4H3S)2]- to the anionic 2 in THF resulted
in formation of a linear trinuclear complex [(CO)3Mn(µ-2-S-C4H3S)3Ni(µ-2-S-C4H3S)3Mn-
(CO)3]2- (4) possessing a homoleptic hexathiolatonickel(II) core. It seems reasonable to
conclude that the d6 Mn(I) [(2-S-C4H3S)3Mn(CO)3]2- fragment is isolobal with the d6 Fe(II)
[(ER)3Fe(CO)3]- fragment in complexes 4, 3, and 2.
In tr od u ction
To our knowledge, a few examples of complexes contain-
ing a homoleptic hexathiolatometal core or hexaseleno-
latometal core are reported and characterized by X-ray
crystallography.3
The study of nickel thiolate and selenolate chemistry
has been actively pursued,1 motivated primarily by the
relevance of such biomimetic nickel/nickel-iron com-
plexes to [NiFe] hydrogenases and CO dehydrogenase.2
Recent work in this laboratory showed that cis-[Mn-
(CO)4(ER)2]- and fac-[Fe(CO)3(SePh)3]- complexes are
useful in the syntheses of heterotrimetallic Mn(I)-Co-
(III)-Mn(I)-chalcogenolate complexes [(CO)4Mn(µ-ER)2-
Co(CO)(µ-E′R)3Mn(CO)3] (E ) E′ ) Te, R ) Ph; E ) Te,
E′ ) Se, R ) Ph; E ) E′ ) Se, R ) Me) with a unique
Co(III)-CO bond,4 and [(CO)3M(µ-SePh)3M′(µ-SePh)3M-
(CO)3]-1/0 (M ) Mn, M′ ) Co; M ) Fe, M′ ) Fe, Cd, Zn,
Ni) with a homoleptic hexaselenolatometal core.3b,5 In
these reactions, the complexes fac-[Fe(CO)3(SePh)3]-
and cis-[Mn(CO)4(ER)2]- act as potential “chelating
metallo ligands” and selenolate ligand-transfer rea-
gents.5c,6
† Department of Chemistry, National Changhua University of
Education.
§ Department of Physics, National Changhua University of Educa-
tion.
‡ National Taiwan University.
(1) (a) Arnold, J . In Progress in Inorganic Chemistry; Karlin, K. D.,
Ed.; J ohn Wiley & Sons: New York, 1995; Vol. 43, p 353. (b) Halcrow,
M. A.; Christou, G. Chem. Rev. 1994, 94, 2421. (c) Tucci, G. C.; Holm,
R. H. J . Am. Chem. Soc. 1995, 117, 6489. (d) Osterloh, F.; Saak, W.;
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Whitehead, J . P.; Maroney, M. J . J . Am. Chem. Soc. 1993, 115, 3576.
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Mascharak, P. K. J . Am. Chem. Soc. 1995, 117, 1584. (g) Lai, C.-H.;.
Reibenspies, J . H.; Darensbourg, M. Y. Angew. Chem., Int. Ed. Engl.
1996, 35, 2390. (h) Nguyen, D. H.; Hsu, H.-F.; Millar, M.; Koch, S. A.;
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8963.
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Hu, Z. G.; Spangler, N. J .; Anderson, M. E.; Xia, J . Q.; Ludden, P. W.;
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A.; Erkens, A.; Schneider, K.; Mu¨ller, A.; Nolting, H.-F.; Sole´, V. A.;
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W.; Plerik, A. J .; Albracht, S. P. J .; Bagley, K. A. Nature 1997, 385,
126.
A recent report on distorted square planar [Ni(CO)-
-
(SPh)n(SePh)3-n
]
(n ) 0, 1, 2), in preparations of the
biomimetic nickel-site structure of [NiFe] hydrogenases
(4) (a) Liaw, W.-F.; Ou, D.-S.; Li, Y.-S.; Lee, W.-Z.; Chuang, C.-Y.;
Lee, Y.-P.; Lee, G.-H.; Peng, S.-M. Inorg. Chem. 1995, 34, 3747. (b)
Liaw, W.-F.; Chuang, C.-Y.; Lee, W.-Z.; Lee, C.-K.; Lee, G.-H.; Peng,
S.-M. Inorg. Chem. 1996, 35, 2530.
(5) (a) Liaw, W.-F.; Lai, C.-H.; Chiang, M.-H.; Lee, C.-K.; Lee, G.-
H.; Peng, S.-M. J . Chem. Soc., Dalton Trans. 1993, 2421. (b) Liaw,
W.-F.; Chiang, M.-H.; Liu, C.-J .; Ham, P.-J .; Liu, L.-K. Inorg. Chem.
1993, 32, 1536. (c) Liaw, W.-F.; Chen, C.-H.; Lee, C.-M.; Lin, G.-Y.;
Ching, C.-Y.; Lee, G.-H.; Peng, S.-M. J . Chem. Soc., Dalton Trans. 1998,
353.
(3) (a) Boorman, P. M.; Kraatz, H.-B.; Parvez, M.; Ziegler, T. J .
Chem. Soc., Dalton Trans. 1993, 433. (b) Liaw, W.-F.; Lee, W.-Z.; Wang,
C.-Y.; Lee, G.-H.; Peng, S.-M. Inorg. Chem. 1997, 36, 1253. (c) Leverd,
P. C.; Lance, M.; Nierlich, M.; Vigner, J .; Ephritikhine, M. J . Chem.
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Gindelberger, D. E.; Arnold, J . Inorg. Chem. 1993, 32, 5813.
10.1021/om980833m CCC: $18.00 © 1999 American Chemical Society
Publication on Web 01/27/1999

FeII-NiII-MnI Chalcogenate Complexes
Organometallics, Vol. 18, No. 4, 1999 783
[Fe(CO)3(ER)3]- in THF,5ab,11 was isolated and recrys-
tallized from THF/hexane (85% for 3) (Scheme 1c,d). The
well-known dimer [(CO)4Mn(µ-2-S-C4H3S)2Mn(CO)4] was
obtained as a byproduct (hexane/THF soluble) during
the isolation of complex 3.12 IR ν(CO) data (the carbonyl
stretching bands 2061 m, 2007 sh cm-1 of complex 3,
comparing to ν(CO) (2070 s, 2019 s cm-1) of complex
(CO)3Fe(µ-SePh)3NiII(µ-SePh)3FeII(CO)3,5c were assigned
to the FeII(CO)3 fragment, and the stretching bands
1998 vs, 1904 s cm-1, comparing to the ν(CO) (1994 vs,
1914 s cm-1) in the [(CO)3Mn(µ-2-S-C4H3S)3Mn(CO)3]-,
were attributed to the CO stretching bands of the MnI-
(CO)3 fragment of complex 3) suggested its formulation
as the PPN+ salt of [(CO)3Mn(µ-2-S-C4H3S)3Ni(µ-
SePh)3Fe(CO)3]- with the central NiII surrounded by
three bridging [S-C4H3S]- ligands and three bridging
[SePh]- ligands, which was also confirmed by X-ray
crystallography. A reasonable reaction sequence ac-
counting for the formation of heterotrinuclear [(CO)3Mn-
(µ-2-S-C4H3S)3Ni(µ-ER)3Fe(CO)3]- is shown in Scheme
1c,d. Cleavage of the MnI-S bond in complex 1 by an
incoming tridentate metallo ligand fac-[Fe(CO)3(ER)3]-
led to the presumed intermediate [(CO)4Mn(µ-2-S-
C4H3S)2Ni(2-S-C4H3S)(µ-ER)3Fe(CO)3]-, and subsequent
rearrangement of the terminal thiolate ligand [2-S-
C4H3S]- to bridge two metals (MnI and NiII) accompa-
nied by dissociation of a labile carbonyl from MnI yielded
the anionic [(CO)3Mn(µ-2-S-C4H3S)3Ni(µ-ER)3Fe(CO)3]-.
These results established that the same stoichiometric
quantities of [(CO)3Mn(µ-2-S-C4H3S)3Ni(µ-ER)3Fe(CO)3]-
are formed concurrently with [(CO)4Mn(µ-2-S-C4H3S)2-
Mn(CO)4] dimer. When attempting to isolate complex
2 by drying under vacuum and extracting with THF,
we isolated only an insoluble solid. We conclude that
the replacement of the selenolate ligands with thiolate
ligands in complex [(CO)3Mn(µ-2-S-C4H3S)3Ni(µ-
SePh)3Fe(CO)3]- has a significant effect on its thermal
stability.
Sch em e 1
and CO dehydrogenase,2 has prompted us to synthesize
Ni-Fe-thiolate complexes.7 Our efforts toward the
preparations of FeII-NiII-chalcogenolate complexes pro-
vide the first example of heterotrimetallic FeII-NiII-
MnI-chalcogenolate complexes with a heteroleptic/
homoleptic hexachalcogenolatonickel(II) core and MnI-
NiII-MnI-thiolate complexes with a homoleptic hexathio-
latonickel(II) core.
Resu lts a n d Discu ssion
When a THF solution of di(2-thienyl) disulfide and
[PPN][Mn(CO)5] are stirred under N2,8 a rapid reaction
ensues over the course of 5 min at ambient temperature
to give the yellow cis-[PPN][Mn(CO)4(2-S-C4H3S)2],9,10
in 90% isolated yield after removal of [PPN][(CO)3Mn-
(µ-2-S-C4H3S)3Mn(CO)3] by diethyl ether and recrystal-
lization with THF/hexane (Scheme 1a). As illustrated
in Scheme 1b, the reaction of cis-[PPN][Mn(CO)4(2-S-
C4H3S)2] and Ni(ClO4)2‚6H20 in a 2:1 molar ratio in
THF at 10 °C yielded the neutral trinuclear [(CO)4Mn-
(µ-2-S-C4H3S)2Ni(µ-2-S-C4H3S)2Mn(CO)4] (1) (65% yield)
by salt elimination of [PPN][ClO4]. 1H and 13C NMR
spectra show the expected signals for the [2-S-C4H3S]-
ligands in a diamagneic d8 NiII species.
On stirring a 1:1 mixture of complex 2 and cis-[Mn-
(CO)4(2-S-C4H3S)2]- in THF for 3 h at 22 °C, a dark red-
brown solid precipitated, Scheme le. Extracted into
CH3CN, and obtained in crystalline form by diethyl
ether diffusion into CH3CN solution (56% yield), this
compound was analyzed as [PPN]2[(CO)3Mn(µ-2-S-
C4H3S)3Ni(µ-2-S-C4H3S)3Mn(CO)3] (4). The IR ν(CO)
bands (1988 vs, 1892 s cm-1 (CH3CN)) in the solution
spectrum of 4 are indicative of C3v symmetry about Mn
(2A1 + E), as observed in the complex [PPN][(CO)3Mn-
(µ-2-S-C4H3S)3Mn(CO)3] (ν(CO) (THF): 1994 vs, 1914 s
1
cm-1). Complex 4 exhibits a diagnostic H NMR spec-
trum with the 2-thienyl proton resonances well removed
from the diamagnetic region. The protons resonate
downfield, δ 15.20 (br), 13.69 (br) and upfield -12.24
(br) ppm, which is consistent with the central NiII
having a d8 electronic configuration in an octahedral
ligand field. The effective magnetic moment in solid
state by SQUID magnetometer was 3.95 and 3.93 µB
for complexes 3 and 4, respectively. These values are
higher than the spin-only value of 2.83 µB, which are
attributed to the orbital angular momentum. A plot of
ø versus T (5-300 K) indicated no antiferromagnetic
interaction for complexes 3 and 4, respectively.
The dark red [PPN][(CO)3Mn(µ-2-S-C4H3S)3Ni(µ-ER)3-
Fe(CO)3] (E ) S, R ) C4H3S (2); E ) Se, R ) Ph (3)),
formed immediately on reaction of complex 1 and fac-
(7) Liaw, W.-F.; Horng, Y.-C.; Ou, D.-S.; Ching, C.-Y.; Lee, G.-H.;
Peng, S.-M. J . Am. Chem. Soc. 1997, 119, 9299.
(8) Inkrott, K.; Goetze, G.; Shore, S. G. J . Organomet. Chem. 1978,
154, 337.
(9) Liaw, W.-F.; Ching, C.-Y.; Lee, C.-K.; Lee, G.-H.; Peng, S.-M. J .
Chin. Chem. Soc. (Taipei) 1996, 43, 427.
(10) (a) Lyons, L. J .; Tegen, M. H.; Haller, K. J .; Evans, D. H.;
Treichel, P. M. Organometallics 1988, 7, 357. (b) Treichel, P. M.;
Nakagaki, P. C. Organometallics 1986, 5, 711.
(11) Liaw, W.-F.; Lee, G.-H.; Peng, S.-M. To be published.
(12) Abel, E. W.; Dalton, J .; Paul, I.; Smith, J . G.; Stone, F. G. A. J .
Chem. Soc. A 1968, 1203.
The structure of 1 is depicted in Figure 1. The
geometry around the Ni atom is distorted square planar.

784 Organometallics, Vol. 18, No. 4, 1999
Liaw et al.
F igu r e 1. ORTEP drawing and labeling scheme of
[(CO)4Mn(µ-2-S-C4H3S)2Ni(µ-2-S-C4H3S)2Mn(CO)4] with ther-
mal ellipsoids drawn at the 30% probability level.
F igu r e 2. ORTEP drawing and labeling scheme of
[(CO)3Mn(µ-2-S-C4H3S)3Ni(µ-SePh)3Fe(CO)3]- with thermal
ellipsoids drawn at the 30% probability level.
Further examination shows that there is no significant
NiII‚‚‚MnI bonding (NiII‚‚‚MnI(A) 3.364 Å and NiII‚‚‚MnI-
(B) 3.364 Å), and the four-membered NiS2Mn rings are
decidedly bent with a dihedral angle between MnS2 and
NiS2 planes of 32.74°. In comparison, the heterotri-
nuclear complex [{Cp2Nb(µ-SMe)2}2Ni]2+ has the Ni0
atom in an approximately tetrahedral arrangement of
the bridging thiolates and Ni0-NbIV metal-metal
bonds.13 The dependence of geometry on electron popu-
lation (d8 NiII) and the longer NiII‚‚‚MnI distances are
adopted to rationalize the construction of complex 1 with
a square planar NiII-thiolate core. The average NiII-S
bond of length 2.217(8) Å is shorter than the terminal
NiII-S distances in distorted tetrahedral [Ni(SPh)4]2-
(average 2.281(1) Å).14 The intramolecular S‚‚‚S contact
distances in 1 are in the range 2.980-3.059 Å, indicative
of the absence of direct S-S bonding.
The molecular structure of 3 is shown in Figure 2,
with selected bond distances and angles collected in
Table 3. Complex 3 has a linear chain of one nickel(II),
one iron(II), and one manganese(I) atom; the central NiII
atom lies in a slightly distorted octahedral environment
of selenium and sulfur atoms (NiS3Se3 core) provided
by two facially coordinating tridentate [(PhSe)3FeII-
(CO)3] and [(2-S-C4H3S)3MnI(CO)3] fragments. The av-
erage NiII-S bond of length 2.451(2) Å is significantly
longer than that of complex 1 (average 2.217(8) Å). The
NiII-Se bond lengths range from 2.556(2) to 2.568(2) Å
(average ) 2.564(2) Å). These are longer than the NiII-
Se distances reported in tetrahedral [Ni(SePh)4]2- (Ni-
Seav ) 2.401(3) Å)15 and distorted square planar
[Ni(CO)(SePh)3]- (Ni-Seav ) 2.317(2) Å).7 The NiII‚‚‚
FeII distance, 3.340 Å, and NiII‚‚‚MnI distance, 3.192 Å,
exclude any direct metal-metal interactions. It is
noteworthy that NiII-S, NiII-Se, NiII‚‚‚MnI, and NiII‚‚
Ta ble 1. Cr ysta llogr a p h ic Da ta of Com p lexes (a ) 1
a n d (b) 3‚3THF
1
3‚3THF
chem formula
fw
cryst syst
space group
λ, Å (Mo KR)
a, Å
C24H12O8Mn2NiS8 C84H78O9P2FeMnNiS6NSe3
853.41
triclinic
P1h
1906.15
orthorhombic
Pca21
0.7107
24.8147(4)
12.9101(2)
27.0074(5)
90
0.7107
8.4017(1)
9.2691(1)
11.3735(1)
68.345(1)
79.851(1)
78.049(1)
800.51(2)
1
b, Å
c, Å
R, deg
â, deg
90
90
γ, deg
V, Å3
8652.1(3)
4
Z
F
calcd, g cm-3
1.770
1.463
µ, cm-1
19.25
20.23
F(000)
426
3872
no. of measd
reflcns
10 563
50 752
no. of obsd
reflcns
no. of refined
params
3663
197
15 397
905
T, °C
22
22
R [I > 2σ(I)]
0.0435a
0.1320b
0.0727a
0.1822b
2
RwF
R ) ∑|(|Fo| - |Fc|)|/∑|Fo|, RwF ) {∑w(Fo2 - Fc2)2/∑[w(Fo2)2]}1/2
.
a
b
2
‚FeII distances of 2.451(2), 2.564(2), 3.192, and 3.340 Å,5c
respectively, also support the formation of complex 3
as a heterotrinuclear FeII-NiII-MnI-mixed-chalcogeno-
late complex, consistent with the conclusion in IR ν(CO)
data.
The X-ray structural analysis (Figure 3) of complex
4, isostructural with complex 3, reveals a centrosym-
metric trinuclear manganese-nickel-manganese-thi-
olate complex in which the NiII is in a distorted
octahedral arrangement with the sulfur atoms of thi-
olates in two parallel faces of the octahedron capped by
tricarbonylmanganese(I) fragments. The NiS6 core has
(13) (a) Prout, K.; Critchley, S. R.; Rees, G. V. Acta Crystallogr. Sec.
B 1974, 30B, 2305. (b) Blower, P. J .; Dilworth, J . R. Coord. Chem. Rev.
1987, 76, 121.
(14) Swenson, D.; Baezinger, N. C.; Coucouvanis, D. J . Am. Chem.
Soc. 1978, 100, 1932.
(15) Goldman, C. M.; Olmstead, M. M.; Mascharak, P. K. Inorg.
Chem. 1996, 35, 2752.

FeII-NiII-MnI Chalcogenate Complexes
Organometallics, Vol. 18, No. 4, 1999 785
Ta ble 2. Cr ysta llogr a p h ic Da ta of Com p lex
4‚2CH3CN
chem formula
fw
cryst syst
space group
λ, Å (Mo KR)
a, Å
C106H84N4O6P4Mn2NiS12
2187.03
triclinic
P1h
0.7107
12.575(3)
14.176(4)
16.156(3)
70.37(2)
85.54(2)
76.92(2)
2642.2(11)
1
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
F
calcd, g cm-3
1.375
7.428
1129
µ, cm-1
F(000)
no. of measd reflcns
9288
no. of obsd reflcns (I > 2σ(I))
no. of refined params
7002
611
T, °C
25
0.043
0.041
Ra
b
Rw
a
b
2 1/2
R ) ∑|(Fo - Fc)|/ ∑Fo. R ) [∑(w(Fo - Fc)2/wFo
] .
Ta ble 3. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for (a ) Com p lex 1 a n d (b) Com p lex 3‚3THF
F igu r e 3. ORTEP drawing and labeling scheme of
[(CO)3Mn(µ-2-S-C4H3S)3Ni(µ-2-S-C4H3S)3Mn(CO)3]2- with
thermal ellipsoids drawn at the 30% probability level.
(a) Complex 1
Ni-S(1)
2.217(1)
2.382(1)
Ni-S(3)
2.216(1)
2.391(1)
prepared by employing fac-[Fe(CO)3(2-S-C4H3S)3]-/cis-
[Mn(CO)4(2-S-C4H3S)2]- serving as a chelating metallo
ligand and intermetal ligand transfer reagent under
mild conditions. Also, it seems reasonable to state that
the anionic [(CO)3Mn(µ-2-S-C4H3S)3Ni(µ-SePh)3Fe(CO)3]-
bears a close structural resemblance to [(CO)3Mn(µ-2-
S-C4H3S)3Ni(µ-2-S-C4H3S)3Mn(CO)3]2-, in which the d6
Mn(I) [(2-S-C4H3S)3Mn(CO)3]2- fragment is isolobal with
the d6 Fe(II) [(ER)3Fe(CO)3]- fragment of [(CO)3Mn(µ-
2-S-C4H3S)3Ni(µ-ER)3Fe(CO)3]-.
Mn-S(1)
Mn-S(3)
S(3A)-Ni-S(3)
S(3)-Ni-S(1)
S(3)-Ni-S(1A)
S(4)-C(9)-S(3)
180.0
S(1)-Mn-S(3)
Ni-S(1)-Mn
Ni-S(3)-Mn
S(2)-C(5)-S(1)
77.28(3)
93.93(3)
93.72(3)
125.2(2)
84.47(3)
95.53(3)
124.7(2)
(b) Complex 3‚3THF
Ni-S(1)
Ni-S(3)
Ni-Se(2)
Fe-Se(1)
Fe-Se(3)
Mn-S(2)
2.430(2)
2.499(2)
2.568(2)
2.436(2)
2.422(2)
2.409(2)
Ni-S(2)
2.424(2)
2.556(2)
2.567(2)
2.438(2)
2.419(2)
2.453(2)
Ni-Se(1)
Ni-Se(3)
Fe-Se(2)
Mn-S(1)
Mn-S(3)
S(1)-Ni-S(2)
S(1)-Ni-Se(1)
S(1)-Ni-Se(3)
Se(1)-Ni-Se(3)
Mn-S(1)-Ni
81.18(7)
175.07(7)
98.96(7)
77.00(5)
82.33(7)
81.72(8)
S(1)-Ni-S(3)
S(1)-Ni-Se(2)
Se(1)-Ni-Se(2)
Fe-Se(1)-Ni
81.67(7)
102.91(6)
79.07(5)
83.95(5)
84.01(5)
Exp er im en ta l Section
Manipulations, reactions, and transfers of samples were
conducted under nitrogen according to standard Schlenk
techniques or in a glovebox (Ar gas). Solvents were distilled
under nitrogen from appropriate drying agents (diethyl ether
from CaH2; acetonitrile from CaH2/P2O5; hexane and tetrahy-
drofuran (THF) from Na/benzophenone) and stored in dried,
N2-filled flasks over 4 Å molecular sieves. A nitrogen purge
was used on these solvents before use, and transfers to reaction
vessels were via stainless-steel cannula under N2 at a positive
pressure. The reagents dimanganese decacarbonyl, iron pen-
tacarbonyl, bis(triphenylphosphoranylidene)ammonium chlo-
ride, di(2-thienyl) disulfide, diphenyl diselenide, and nickel
perchlorate (Aldrich) were used as received. Infrared spectra
were recorded on a spectrometer (Bio-Rad FTS-185) with
sealed solution cells (0.1 mm) and KBr windows. UV-visible
spectra were recorded on a GBC 918 spectrophotometer. In
NMR spectra (recorded on a Bruker AC 200 spectrometer),
chemical shifts of 1H and 13C are relative to tetramethylsilane.
Magnetic susceptibilities were carried out in the temperature
range 300-5 K on a Quantum Design MPMS-5S SQUID
magnetometer. Magnetic data were corrected for diamagnetic
contribution. Analyses of carbon, hydrogen, and nitrogen were
obtained with a CHN analyzer (Heraeus).
Se(1)-Fe-Se(2)
S(1)-Mn-S(2)
φ ) 54° and s/h ) 1.856 (the six-coordinate polyhedron
of D3 symmetry can be defined by the two parameters
φ and s/h, i.e. the twist angle between two parallel
triangular faces of the polyhedron and the ratio of the
side of the triangle to the distance between the tri-
angles),16 and the staggered conformation of two parallel
triangular thiolate faces promises the best minimization
of interactions between the thiolates. The NiII‚‚‚MnI
distances, average 3.201 Å (NiII‚‚‚MnI(1) 3.201 Å and
NiII‚‚‚MnI(2) 3.201 Å), is not short enough to suggest a
bonding interaction between the two metals. The mean
NiII-S bond of length 2.443(1) Å and NiII‚‚‚MnI distance
of 3.201 Å are comparable with the average NiII-S bond
length of 2.451(2) Å and the NiII‚‚‚MnI distance of 3.192
Å in complex 3, respectively.
In summary, the heterotrimetallic complexes 1, 2, 3,
and 4 possessing a homoleptic hexathiolatonickel(II)/
heteroleptic hexachalcogenolatonickel(II) core have been
P r ep a r a tion of cis-[P P N][Mn (CO)4(2-SC4H3S)2].9 [PPN]-
[Mn(CO)5] (0.6 mmol, 0.440 g)8 dissolved in THF (3 mL) was
stirred under N2, and di(2-thienyl) disulfide (0.6 mmol, 0.138
g) in THF solution was added to the [PPN][Mn(CO)5] solution
by cannula under positive N2 at 10 °C. After stirring of the
reaction solution for 5 min, a bright yellow solid precipitated
(16) (a) Stiefel, E. I.; Brown, G. F. Inorg. Chem. 1972, 11, 434. (b)
McCleverty, J . A. Prog. Inorg. Chem. 1968, 10, 49. (c) Eisenberg, R.
Prog. Inorg. Chem. 1970, 12, 295. (d) Keppert, D. L. Prog. Inorg. Chem.
1977, 23, 1.

786 Organometallics, Vol. 18, No. 4, 1999
Liaw et al.
Ta ble 4. Selected Bon d Dista n ces (Å) a n d An gles
cannula under positive N2 at 10 °C. After stirring of the
reaction solution for 30 min, a dark red product [PPN]-
[(CO)3Mn(µ-2-S-C4H3S)3Ni(µ-SePh)3Fe(CO)3] (3) precipitated
on addition of hexane (15 mL) at 10 °C. The product 3 was
isolated by removing the solvent and recrystallizing from THF/
hexane (0.145 g, 85%). Complex 3: IR (νCO) (THF): 2061 m,
2007 sh, 1998 vs, 1904 s cm-1. 1H NMR (C4D8O): δ 16.35 (br),
12.84 (br) ppm (SC4H3S); 14.87 (br), 7.62-6.80 ppm (Ph).
Absorption spectrum (THF) [λmax, nm (ꢀ, M-1 cm-1)]: 674(210).
Anal. Calcd for C72H54NO6P2S6Se3NiMnFe: C, 51.18; H, 3.22;
N, 0.83. Found: C, 51.35; H, 3.37; N, 1.00. The compound
[PPN][(CO)3Mn(µ-2-S-C4H3S)3Ni(µ-2-S-C4H3S)3Fe(CO)3] (2) (IR
(νCO) (THF): 2073 m, 2017 sh, 1998 vs, 1906 s cm-1) is unstable
in THF solution and decomposes over a period of several hours
at room temperature. When attempting to isolate complex 2
by drying under vacuum and extracting with THF, we isolated
only the decomposition solid.
P r ep a r a t ion of [P P N]2[(CO)3Mn (µ-2-S-C4H 3S)3Ni(µ-2-
S-C4H3S)3Mn (CO)3] (4). cis-[PPN][Mn(CO)4(2-S-C4H3S)2] (0.094
g, 0.1 mmol) in THF solution was added to compound 2 (0.156
g, 0.1 mmol) in THF solution dropwise under N2 at room
temperature. The reaction solution was stirred for 3 h, and
the dark red-brown product [PPN]2[(CO)3Mn(µ-2-S-C4H3S)3Ni-
(µ-2-S-C4H3S)3Mn(CO)3] (4) precipitated. The brown solution
was removed under positive N2, then complex 4 was washed
with THF twice and dried under vacuum (0.123 g, 56%).
Diffusion of diethyl ether into a solution of complex 4 in CH3-
CN at -15 °C for 3 weeks led to dark red-brown crystals
suitable for X-ray crystallography. IR (νCO) (CH3CN): 1988 vs,
1892 s cm-1. 1H NMR (CD3CN): δ 15.20 (br), 13.69 (br), -12.24
(br) ppm (SC4H3S); 7.60-7.04 ppm (Ph). Absorption spectrum
(CH3CN) [λmax, nm (ꢀ, M-1 cm-1)]: 405(8417), 494(2728). Anal.
Calcd for C106H84N4O6P4S12Mn2Ni: C, 58.22; H, 3.87; N, 2.56.
Found: C, 58.09; H, 3.88; N, 2.66. The compound 4 is unstable
in CH3CN solution and decomposes overnight at room tem-
perature.
Cr ysta llogr a p h y. Crystallographic data for complexes 1,
3, and 4 are collected in Tables 1 and 2, and in the Supporting
Information. All crystals were chunky: 1, dark red, ca. 0.22
× 0.20 × 0.10 mm; 3, dark red, 0.40 × 0.40 × 0.10 mm; 4,
dark red brown, 0.50 × 0.50 × 0.50 mm. Each was mounted
on a glass fiber and quickly coated in epoxy resin. Diffraction
measurements for complexes 1 and 3 were carried out at 25
°C on a Siemens SMART CCD diffractometer (λ 0.7107 Å) with
graphite-monochromated Mo KR radiation (λ 0.7107 Å) with
θ between 1.94° and 27.48° for complex 1, 1.51° < θ < 25.09°
for complex 3. A SADABS absorption correction was made. The
SHELXTL program was employed. In the structure determi-
nation, the positions of Fe and Mn atoms are determined on
the basis of the synthetic route, not from the X-ray diffraction
data for complex 3. The unit-cell parameters were obtained
by the least-square refinement from 25 reflections with 2θ
between 14.68° and 26.84° for 4. Diffraction measurements
for complex 4 was carried out at 25 °C on a Nonius CAD 4
diffractometer with graphite-monochromated Mo KR radiation
(λ 0.7107 Å) employing the θ-2θ scan mode.17 A ψ-scan
absorption correction was made. Structural determinations
were made using the NRCC-SDP-VAX package of pro-
grams.18,19 Selected bond distances and angles are listed in
Tables 3 and 4.
(d eg) for Com p lex 4‚2CH3CN
Ni-S(1)
Ni-S(5)
Mn-S(3)
2.427(1)
2.437(1)
2.396(1)
Ni-S(3)
Mn-S(1)
Mn-S(5)
2.466(1)
2.391(1)
2.419(1)
S(1)-Ni-S(3)
S(1)-Ni-S(1a)
S(1)-Ni-S(5a)
S(1)-Mn-S(5)
100.18(4)
179.9
80.59(3)
81.69(4)
S(1)-Ni-S(5)
S(1)-Ni-S(3a)
S(1)-Mn-S(3)
Ni-S(1)-Mn
99.41(3)
79.82(4)
81.98(4)
83.29(4)
on addition of hexane (15 mL) at 10 °C. The solid was isolated
by removing the solvent. Since the thermally unstable cis-
[PPN][Mn(CO)4(2-S-C4H3S)2] partially transformed into [PPN]-
[(CO)3Mn(µ-2-S-C4H3S)3Mn(CO)3] in THF at ambient temper-
ature, diethyl ether was added to separate cis-[PPN][Mn(CO)4(2-
S-C4H3S)2] (soluble in diethyl ether) and [PPN][(CO)3Mn(µ-2-
S-C4H3S)3Mn(CO)3] (insoluble in diethyl ether) characterized
by IR (IR (νCO) (THF): 1994 vs, 1914 s cm-1) and X-ray
crystallography (the complex crystallized in orthorhombic
space group Pna21 with a ) 29.371(4) Å, b ) 10.904(2) Å, c )
18.179(3) Å, V ) 5821.9(16) Å3, F(000) ) 2531, Z ) 4, dcalc
)
1.866 g cm-3, final R ) 0.039, and RwF ) 0.040). The yield of
product cis-[PPN][Mn(CO)4(2-S-C4H3S)2] was 0.506 g (90%). IR
(νCO) (THF): 2055 m, 1980 s, 1958 m, 1917 m cm-1. Absorption
spectrum (THF) [λmax, nm (ꢀ, M-1 cm-1)]: 266(13638), 274-
(12202), 289(9252), 303(8853), 410(958).9
Ca u tion : Perchlorate salts of metal complexes with organic
ligands are potentially explosive; only small amounts of
material should be prepared and handled with great caution.
P r ep a r a t ion
of
[(CO)4Mn (µ-2-S-C4H 3S)2Ni(µ-2-S-
C4H3S)2Mn (CO)4] (1). The complex cis-[PPN][Mn(CO)4(2-S-
C4H3S)2] (0.4 mmol, 0.375 g) dissolved in THF (5 mL) was
stirred under N2, and Ni(ClO4)2‚6H2O (0.2 mmol, 0.073 g) in
THF solution was added by cannula under positive pressure
of N2 at 10 °C. After stirring for 5 min, hexane (10 mL) was
added, and the dark red solution was filtered to remove [PPN]-
[ClO4]. The filtrate (in THF + hexane) was dried under
vacuum, and diethyl ether was added to separate product
[(CO)4Mn(µ-SC4H3S)2Ni(µ-SC4H3S)2Mn(CO)4] (1) (diethyl ether
soluble) and the [(CO)3Mn(µ-SC4H3S)3Mn(CO)3]- (IR (νCO
)
(THF): 1914 s, 1994 vs cm-1; diethyl ether insoluble).10 The
yield of dark red complex 1 was 0.111 g (65%). The dark red
complex 1, dissolved in diethyl ether solution and stored for 3
weeks at -15 °C, led to formation of dark red crystals of 1
suitable for X-ray crystallography. IR (νCO): 2082 m, 2010 s,
2001 sh, 1966 m cm-1 (THF); 2082 m, 2013 s, 2001 m, 1969 m
cm-1 (diethyl ether). 1H NMR (C4D8O): δ 7.46 (d), 7.45 (d),
7.26 (d), 7.25 (d), 6.36 (d), 6.34 (d) ppm (SC4H3S). 13C NMR
(C4D8O): δ 127.90, 129.37, 135.04 ppm (SC4H3S). Absorption
spectrum (THF) [λmax, nm (ꢀ, M-1 cm-1)]: 449(6921), 523(4013).
Anal. Calcd for C24H12O8Mn2NiS8: C, 33.78; H, 1.42. Found:
C, 33.62; H, 1.39. The analogue [(CO)4Mn(µ-SPh)2Ni(µ-SPh)2Mn-
(CO)4] (IR (νCO) (THF): 2079 m, 2002 vs, 1990 sh, 1960 m cm-1
)
is extremely unstable and decomposes under prolonged vacuum.
The IR spectrum revealed that the neutral [(CO)4Mn(µ-
SPh)2Ni(µ-SPh)2Mn(CO)4] converted to the well-known [(CO)3-
Mn(µ-SPh)3Mn(CO)3]- (IR (νCO) (THF): 1907 vs, 1987 s cm-1
)
and insoluble solid.10
P r ep a r a tion of [P P N][(CO)3Mn (µ-2-S-C4H3S)3Ni(µ-
ER)3F e(CO)3] (E ) S, R ) C4H3S (2); E ) Se, R ) P h (3)).
Compound 1 (0.094 g, 0.1 mmol) dissolved in THF (2 mL) was
stirred under N2, and fac-[PPN][Fe(CO)3(SePh)3] (0.115 g, 0.1
mmol; or fac-[PPN][Fe(CO)3(2-S-C4H3S)3], 0.102 g, 0.1 mmol)5
in THF solution was slowly added to compound 1 solution by
Ack n ow led gm en t. The support of the National
Science Council (Taiwan) is gratefully acknowledged.
Su p p or tin g In for m a tion Ava ila ble: An X-ray crystal-
lographic file for the structure determinations of [(CO)4Mn-
(µ-2-S-C4H3S)2Ni(µ-2-S-C4H3S)2Mn(CO)4], [PPN][(CO)3Mn(µ-2-
S-C4H3S)3Ni(µ-SePh)3Fe(CO)3], and [PPN]2[(CO)3Mn(µ-2-S-
C4H3S)3Ni(µ-2-S-C4H3S)3Mn(CO)3]. This material is available
free of charge via the Internet at http://pubs.acs.org.
(17) North, A. C. T.; Philips, D. C.; Mathews, F. S. Acta Crystallogr.
1968, A24, 351.
(18) Gabe, E. J .; LePage, Y.; Chrarland, J . P.; Lee, F. L.; White, P.
S. J . Appl. Crystallogr. 1989, 22, 384.
(19) Atomic scattering factors were obtained from the following:
International Tables for X-Ray Clystallography; Kynoch Press: Bir-
mingham, England, 1974; Vol. IV.
OM980833M