S-S Bond-activation of diorganyl disulfide by anionic [Mn(CO)5]-: Crystal structures of [MnII(-SC5H4NO-)3]- and [(CO)3Mn(μ-SR)3Co(μ-SR)3Mn(CO) 3]- (R=C6H4NHCOPh)

Article abstract of DOI:10.1016/S0020-1693(02)00733-8

The S-S bond-activation of diorganyl disulfide by the anionic metal carbonyl fragment [Mn(CO)₅]^- gives rise to an extensive chemistry. Oxidative decarbonylation addition of 2,2′-dithiobis(pyridine-N-oxide) to [Mn(CO)₅]^-, followed by chelation and metal-center oxidation, led to the formation of [Mn^II(-SC₅H₄NO-)₃]^- (1). The effective magnetic moment in solid state by SQUID magnetometer was 5.88 μ_B for complex 1, which is consistent with the Mn^II having a high-spin d⁵ electronic configuration in an octahedral ligand field. The average Mn(II)-S, S-C and N-O bond lengths of 2.581(1), 1.692(4) and 1.326(4) A, respectively, indicate that the negative charge of the bidentate 1-oxo-2-thiopyridinato [SC₅H₄NO]^- ligand in complex 1 is mainly localized on the oxygen atom. The results are consistent with thiolate-donor [-SC₅H₄NO]^- stabilization of the lower oxidation state of manganese (Mn(I)), while the O,S-chelating [-SC₅H₄NO-]^- ligand enhances the stability of manganese in the higher oxidation state (Mn(II)). Activation of S-S bond as well as O-H bond of 2,2′-dithiosalicylic acid by [Mn(CO)₅]^- yielded [(CO)₃Mn(μ-SC₆H₄-C(O)-O-)₂Mn (CO)₃]^2- (4). Oxidative addition of bis(o-benzamidophenyl) disulfide to [Mn(CO)₅]^- resulted in the formation of cis-[Mn(CO)₄(SR)₂]^- (R=C₆H₄NHCOPh) which was employed as a chelating metallo ligand to synthesize heterotrinuclear [(CO)₃Mn(μ-SR)₃Co(μ-SR)₃Mn(CO) ₃]^- (8) possessing a homoleptic hexathiolatocobalt(III) core.

Full text of DOI:10.1016/S0020-1693(02)00733-8

Inorganica Chimica Acta 332 (2002) 153ꢂ159
/
www.elsevier.com/locate/ica
Sꢀ
/
S Bond-activation of diorganyl disulfide by anionic [Mn(CO)5]ꢀ:
crystal structures of [MnII(ꢀ )3]ꢀ and [(CO)3Mn(m-
SC5H4NOꢀ
SR)3Co(m-SR)3Mn(CO)3]ꢀ (Rꢁ
C6H4NHCOPh)
/
/
/
Wen-Feng Liaw a,*, Chung-Hung Hsieh a, Shie-Ming Peng b, Gene-Hsiang Lee b
a Department of Chemistry, National Changhua University of Education, Changhua 50058, Taiwan, ROC
b Department of Chemistry and Instrumentation Center, National Taiwan University, Taipei 10764, Taiwan, ROC
Received 1 October 2001; accepted 24 December 2001
Abstract
The Sꢀ
/
S bond-activation of diorganyl disulfide by the anionic metal carbonyl fragment [Mn(CO)5]ꢀ gives rise to an extensive
chemistry. Oxidative decarbonylation addition of 2,2?-dithiobis(pyridine-N-oxide) to [Mn(CO)5]ꢀ, followed by chelation and metal-
center oxidation, led to the formation of [MnII(ꢀ
/
SC5H4NOꢀ
/
)3]ꢀ (1). The effective magnetic moment in solid state by SQUID
magnetometer was 5.88 mB for complex 1, which is consistent with the MnII having a high-spin d5 electronic configuration in an
˚
octahedral ligand field. The average Mn(II)ꢀ
/
S, Sꢀ
/
C and Nꢀ
/
O bond lengths of 2.581(1), 1.692(4) and 1.326(4) A, respectively,
indicate that the negative charge of the bidentate 1-oxo-2-thiopyridinato [SC5H4NO]ꢀ ligand in complex 1 is mainly localized on the
oxygen atom. The results are consistent with thiolate-donor [ꢀ
SC5H4NO]ꢀ stabilization of the lower oxidation state of manganese
(Mn(I)), while the O,S-chelating [ꢀSC5H4NOꢀ
ꢀ ligand enhances the stability of manganese in the higher oxidation state (Mn(II)).
Activation of SꢀS bond as well as Oꢀ C(O)ꢀ
H bond of 2,2?-dithiosalicylic acid by [Mn(CO)5]ꢀ yielded [(CO)3Mn(m-SC6H4ꢀ
Oꢀ
)2Mn(CO)3]2ꢀ (4). Oxidative addition of bis(o-benzamidophenyl) disulfide to [Mn(CO)5]ꢀ resulted in the formation of cis-
[Mn(CO)4(SR)2]ꢀ (Rꢁ
/
/
/]
/
/
/
/
/
/C6H4NHCOPh) which was employed as a chelating metallo ligand to synthesize heterotrinuclear
[(CO)3Mn(m-SR)3Co(m-SR)3Mn(CO)3]ꢀ (8) possessing a homoleptic hexathiolatocobalt(III) core. # 2002 Published by Elsevier
Science B.V.
Keywords: Manganese(II)ꢂ
/
thiolate; Sꢀ
/
S Bond-activation; Heterotrinuclear Mnꢀ
/
Coꢀ
/
Mnꢀthiolate
/
1. Introduction
coordinate MnI complex fac-[Mn(CO)3(ꢀ
/
SC5H4Nꢀ
/
)(ꢀ
/
SC5H4N)]ꢀ prepared from the reaction of [Mn(CO)5]ꢀ
and bis(2-pyridyl) disulfide by oxidative addition and
the subsequent chelation (Scheme 1(c)) [4], the forma-
tion of the five-coordinate MnI complex [Mn(CO)3-
Anionic metal carbonyls are known to function as
nucleophiles and show a range of reactivity that depends
on its substituents, the ligand environment, the metal,
and its oxidation state [1]. Recently, the reaction of the
anionic metal carbonyl fragment [Mn(CO)5]ꢀ has been
(ꢀ
/
EC6H4NHꢀ
/
)]ꢀ (Eꢁ
S, Se, Te) in the reaction of
/
[Mn(CO)5]ꢀ with 2-aminophenyl dichalcogenides by
combining the dichalcogen synthetic methodology with
the terminal chalcogenolate ligand oxidation followed
by deprotonation (Scheme 1(d)) [5], a nucleophilic
shown to give rise to an extensive chemistry [2ꢂ8]. Some
/
known reactions are outlined in Scheme 1: oxidative
addition of diorganyl dichalcogenides to [Mn(CO)5]ꢀ
affording cis-[Mn(CO)4(ER)2]ꢀ (Eꢁ
yl, alkyl) (Scheme 1(a)) [2], coordinative addition of
/
Se, Te; Rꢁphen-
/
displacement/a
metathesis
reaction
to
give
[PhSeMn(CO)5] and [Mn2(m-TeMe)2(CO)8], respectively
(Scheme 1(e) and (f)) [2a,6], oxidative addition of 1,2-
benzenedithiol to [Mn(CO)5]ꢀ followed by a Lewis
[Mn(CO)5]ꢀ to TeCl4 to form a discrete chlorotellur-
olate [Cl4Teꢀ
/
Mn(CO)5]ꢀ (Scheme 1(b)) [3], the six-
acidꢂbase reaction to yield the five-coordinate
/
[Mn(CO)3(ꢀ
/
SC6H4Sꢀ
/
)]ꢀ (Scheme 1(g)) [4,7], oxidative
substitution of two CO ligands of [Mn(CO)5]ꢀ by 3,5-
di-tert-butyl-1, 2-benzoquinone (DBBQ) to give
* Corresponding author. Fax: ꢃ886-4-721 1190.
E-mail address: chfeng@cc.ncue.edu.tw (W.-F. Liaw).
0020-1693/02/$ - see front matter # 2002 Published by Elsevier Science B.V.
PII: S 0 0 2 0 - 1 6 9 3 ( 0 2 ) 0 0 7 3 3 - 8

154
W.-F. Liaw et al. / Inorganica Chimica Acta 332 (2002) 153ꢂ159
/
Scheme 1.
[Mn(CO)3(DBCat)]ꢀ (DBCatꢁ
cholate) (Scheme 1(h)) [8].
/
3,5-di-t-butyl-1,2-cate-
Reaction of the anionic [Mn(CO)5]ꢀ with the vari-
eties of diorganyl disulfides has been further investi-
gated. Specifically, the synthesis and characterization of
the
SC5H4NOꢀ
Oꢀ
)2Mn(CO)3]2ꢀ (4) are described. In addition, the
synthesis and structure of a linear trinuclear MnIꢀ
CoIII MnI complex possessing a hexathiolatocobalt(III)
hexacoordinate
MnII
complex
[Mn(ꢀ
/
/
)3]ꢀ (1), and [(CO)3Mn(m-SC6H4ꢀ
/
C(O)ꢀ
/
/
/
ꢀ
/
core, [(CO)3Mn(m-SR)3Co(m-SR)3Mn(CO)3]ꢀ (Rꢁ
/
Scheme 2.
C6H4NHCOPh) (8) is also reported [9]. The variable
valence tris(1-hydroxy-2-pyridinethionato) mangane-
MnII) of intermediate 3, labilizing CO ligands and
se(II,III,IV), characterized by UVꢂVis, EPR, and cyclic
voltammogram, were investigated by Chakravorty and
coworkers [10].
/
ꢀ
accompanied by intermetal [ꢀ
/
SC5H4NOꢀ
/]
ligand
shift, yields complex 1 (Scheme 2(c)) [11].
Compound 1 displays intense charge-transfer transi-
tions at 345, 304, 300 and 294 nm. The electrochemistry
of complex 1, in CH3CN with 0.05 M [Nn-Bu4][PF6] as
supporting electrolyte, reveals two pseudoreversible
2. Results and discussion
redox reactions at ꢀ
/
0.34 and 0.18 V (vs. AgꢂAgNO3),
/
consistent with the observations by Chakravorty and
coworkers [10]. The effective magnetic moment in solid
state by SQUID magnetometer was 5.88 mB for complex
1, which is consistent with the MnII having a high-spin
d5 electronic configuration in an octahedral ligand field.
Alternatively, complex 1 was also obtained by stirring
overnight a mixture of 2 equiv. of 1-hydroxy-2-pyridi-
nethione and [Mn(CO)5]ꢀ in THF at ambient tempera-
ture.
The reaction of 2,2?-dithiobis(pyridine-N-oxide) with
[Mn(CO)5]ꢀ in a 2:1 stoichiometry proceeds cleanly in
dry THF to form anionic tris(1-oxo-2-pyridinethionato)
manganese(II) complex [Mn(ꢀ
/
SC5H4NOꢀ
/
)3]ꢀ (1) iden-
tified by X-ray diffraction analysis. Compound 1 was
isolated as the PPNꢃ salt and a yellow solid from
CH3CNꢂdiethyl ether in 60% yield. This result may be
/
accounted for by the following sequences of reaction
(Scheme 2); the oxidative addition of 2,2?-dithiobis(pyr-
idine-N-oxide) to [Mn(CO)5]ꢀ yields monodentate (S-
Fig. 1 depicts the structure of complex 1 as an ORTEP;
significant bond distances and angles are given in Table
2. The constraints of the bidentate 1-oxo-2-pyridi-
bonded) cis-[Mn(CO)4(ꢀ
2(a)) [2]. Chelation of one terminal thiolate ligand
of intermediate yields the fac-[Mn(CO)3-
(ꢀSC5H4NOꢀ)(ꢀ
SC5H4ꢀNO)]ꢀ (3) where one of the
anionic [ꢀSC5H4NOꢀ
ligands bound to the MnI
/
SC5H4NO)2]ꢀ (2) (Scheme
nethione ligand generate (ca. 76.12(8)8, O(1)ꢀ
S(1); 77.05(7)8, O(2)ꢀMnꢀS(2); and 75.06(7)8, O(3)ꢀ
MnꢀS(3) angles) a severe distortion from octahedron
/
Mnꢀ
/
2
/
/
/
/
/
/
/
/
/
]
at the hexacoordinate manganese(II) sites. The three
sulfur atoms are generally disposed trans to the oxygen
metal in a bidentate manner (S,O-bonded) while the
second one in a monodentate (S-bonded) manner
(Scheme 2(b)) [5,2]. Oxidation of intermediate 3 (by
O2) leads to the formation of complex 1 (Scheme 2(c))
atoms [155.13(9)8, O(1)ꢀ
MnꢀS(1); and 159.36(8)8 O(3)ꢀ
S and three O atoms are in an almost ideal facial
/
Mnꢀ
/
S(3); 162.92(8)8, O(2)ꢀ
/
/
/
MnꢀS(2) angles]. Three
/
[8]. Apparently, the metal-center oxidation (MnI0
/

W.-F. Liaw et al. / Inorganica Chimica Acta 332 (2002) 153ꢂ
/159
155
Table 2
˚
Selected bond distances (A) and bond angles (8) for complexes 1 and 8
Complex 1
Bond distances
MnꢀO(3)
MnꢀO(1)
MnꢀS(2)
S(1)ꢀC(1)
S(3)ꢀC(11)
O(2)ꢀN(2)
2.127(3)
2.156(3)
MnꢀO(2)
MnꢀS(1)
2.172(2)
2.5619(12)
2.6485(13)
1.686(4)
1.325(4)
1.318(3)
2.5331(14) MnꢀS(3)
1.687(4)
1.704(4)
1.334(4)
S(2)ꢀC(6)
O(1)ꢀN(1)
O(3)ꢀN(3)
Bond angles
O(3)ꢀMnꢀO(1)
O(1)ꢀMnꢀO(2)
O(3)ꢀMnꢀS(1)
S(1)ꢀMnꢀS(3)
S(2)ꢀMnꢀS(3)
C(1)ꢀS(1)ꢀMn
90.44(11) O(3)ꢀMnꢀO(2)
89.88(10) O(3)ꢀMnꢀS(2)
85.63(10)
159.36(8)
75.06(7)
95.69(4)
123.8(2)
103.94(8)
87.72(4)
99.74(4)
98.28(14)
O(3)ꢀMnꢀS(3)
S(2)ꢀMnꢀS(1)
N(1)ꢀO(1)ꢀMn
Fig. 1. ORTEP drawing and labeling scheme of [Mn(ꢀSC5H4NOꢀ)3]ꢀ
with thermal ellipsoids drawn at the 30% probability level.
Complex 8
Bond distances
Co(1)ꢀS(1)
Co(1)ꢀS(3)
Mn(1)ꢀS(2A)
2.277(1)
2.299(2)
2.367(2)
Co(1)ꢀS(2A)
Mn(1)ꢀS(1)
Mn(1)ꢀS(3)
2.292(1)
2.373(2)
2.386(2)
Table 1
Crystal data and structure refinement parameters for complexes 1 and
Bond angles
8
S(1)ꢀCo(1)ꢀS(1A)
S(3)ꢀCo(1)ꢀS(1)
S(3)ꢀMn(1)ꢀS(1)
S(2A)ꢀMn(1)ꢀS(1)
180.00(5)
82.94(5)
79.12(5)
78.21(5)
S(3)ꢀCo(1)ꢀS(2)
S(2)ꢀCo(1)ꢀS(1)
S(2A)ꢀMn(1)ꢀS(3)
Co(1)ꢀS(1)ꢀMn(1)
98.21(5)
98.26(4)
78.44(5)
83.96(4)
1
8×2.25THF
Empirical for-
mula
Formula weight 971.95
C
51H42O3N4S3P2Mn C129H108O14.25N7S6P2CoMn2
2407.33
rhombohedral
150 (1)
˚
C distance (1.692(4) A, average) in complex
observed Sꢀ
/
Crystal system
Temperature
monoclinic
295 (2)
1 which indicates the importance of a conjugated
interaction along the ring p-system, the S and O lone-
(K)
˚
l (A) (Mo Ka) 0.7107
0.7107
R3c
˚
C length of 1.692(4) A
pair electrons, and the average Sꢀ
/
Space group
Unit cell dimensions
P21/n
(average) in complex 1 is in agreement with the thione
O bond length
˚
form (Scheme 2(c)) [13]. The average Nꢀ
/
a (A)
10.320(2)
32.2239(2)
32.2239(2)
76.5564(7)
90
˚
˚
of 1.326(4) A is well within the range observed for
b (A)
23.333(4)
19.526(4)
90
˚
c (A)
pyridine 1-oxide [13c], indicating that the negative
ꢀ
a (8)
b (8)
g (8)
charge of the bidentate [ꢀ
/
SC5H4NOꢀ
/]
ligand in
94.593(15)
90
90
120
complex 1 is mainly localized on the oxygen atom
[13d]. The results are consistent with the stabilization
of the lower oxidation state of manganese (Mn(I)) by
3
˚
V (A )
Z
4686.9(14)
4
1.377
68 844.3(9)
24
1.394
Dcalc (g cmꢀ3
)
thiolate-donor [ꢀ
/
SC5H4ꢀNO]ꢀ ligand, while the O,S-
m (cmꢀ1
)
5.31
5.65
chelating [ꢀ
/
SC5H4NOꢀ
/]
ligand enhances the stability
a
R
0.0406
0.0801
Goodness-of-fit 1.021
0.0667
0.1873
1.058
of manganese in the higher oxidation state (MnII)
(Scheme 2) [13].
Under similar reaction condition, the known dianio-
R2WF
b
a
Rꢁaj(jFojꢀjFcj)/ajFoj.
nic dinuclear Mn(I) compound [(CO)3Mn(m-SC6H4ꢀ
/
b
R2WF ꢁ{a[w(Fo2ꢀFc2)2]/a[w(Fo2)2]}1/2
.
C(O)ꢀ
/
Oꢀ
/
)2Mn(CO)3]2ꢀ (4) was obtained from reaction
of 2,2?-dithiosalicylic acid and [Mn(CO)5]ꢀ in THF at
room temperature (r.t.) [14]. A reasonable reaction
sequence accounting for the formation of complex 4 is
environment, individually, with torsion angle 35.678.
The average Mn(II)ꢀS distance of 2.581(1) A in com-
plex 1 is significantly longer than the reported Mn(II)ꢀ
/
/
shown in Scheme 3(a)ꢂ
instead of C(O)OꢀH bond of (SC6H4COOH)2 by
[Mn(CO)5]ꢀ led to the formation of cis-[Mn(CO)4-
OH)2]ꢀ (5), as evident from the IR
/
(c). Activation of Sꢀ
/S bond
˚
A
SPh distance of 2.442(3)
[Mn(SPh)4]2ꢀ [12]. Also, the difference between the
Mn(II)ꢀS and Mn(II)ꢀO lengths is approximately 0.43
A in complex 1, which is not consistent with the
(average) in the
/
/
/
(ꢀ
/
SC6H4ꢀ
/
C(O)ꢀ
/
spectra (THF, cmꢀ1): n(CO) 2073 (w), 2000 (vs), 1979
(m), 1939 (m) which match those of complex cis-
[Mn(CO)4(SPh)2]ꢀ previously established (by IR and
X-ray diffraction) [15]. The elimination of a carbonyl
˚
˚
difference in the covalent radii of S (1.04 A) and O
˚
(0.74 A). In particular, the sum of the covalent radii of C
˚
(0.77 A) and S (1.04 A) is about 0.118 A longer than the
˚
˚

156
W.-F. Liaw et al. / Inorganica Chimica Acta 332 (2002) 153ꢂ159
/
in the presence of cis-[Mn(CO)4(SR)2]ꢀ (Rꢁ
C6H4NHCOPh). Reaction of (RS)2, Co(ClO4)2×6H2O
and cis-[Mn(CO)4(SR)2]ꢀ (Rꢁ
C6H4NHCOPh) in a
/
/
/
0.5:1:2 molar ratio in THF at ambient temperature led
to the formation of [(CO)3Mn(m-SR)3Co(m-SR)3-
Mn(CO)3]ꢀ (8) (Scheme 4). The formation of the stable
complex 8 can be accounted for as: (i) oxidative addition
of bis(o-benzamidophenyl) disulfide to the coordination
compound [(CO)4Mn(m-SR)2CoII(m-SR)2Mn(CO)4] led
to
the
presumed
intermediate
[(CO)4Mn(m-
SR)2CoIII(SR)(m-SR)2Mn(CO)4], (ii) subsequent rear-
rangement of the terminal o-benzamidophenylthiolate
ligand to bridge two metals (Mn and Co) and shift of a
labile carbonyl group from Mn(I) to Co(III) yielded
neutral [(CO)4Mn(m-SR)2Co(CO)(m-SR)3Mn(CO)3] (7)
(Scheme 4(b)) [2], (iii) extended periods of stirring in
THF at r.t., the extremely thermally unstable complex 7
converted into
8
and the known [(CO)3Mn(m-
SR)3Mn(CO)3]ꢀ (9) (Scheme 4(c)) [17]. We attribute
the formation of the heterotrimetallic complex 8 to the
lability of ‘CoIII
CO’ carbonyl group in neutral com-
plex 7 and rapid intermetal transfer of the o-benzami-
dophenylthiolate group. The compound 8 can be
ꢀ
/
crystallized from THFꢂ/hexane after being separated
Scheme 3.
from the CH3CNꢂdiethyl ether-soluble complex 9.
/
The trinuclear dark green anion 8 and the known
brown anion 9, individually, exhibit a two-band pattern
in the n(CO) region of the infrared, but at different
positions, IR (THF, cmꢀ1): n(CO) 2008 (vs), 1929 (s,br)
for 8 and 2001 (vs), 1922 (s,br) for 9, which are
consistent with a tricarbonyl derivative of approxi-
mately C3v symmetry. The 1H NMR spectra of complex
8 shows the expected signals for the phenyl groups
involved and display characteristics of diamagnetic d6
Co(III) and d6 Mn(I) species.
ligand resulting from chelate formation of one terminal
thiolate ligand MnIꢀ
SC6H4COOH of complex 5 yielded
the intermediate fac-[Mn(CO)3(ꢀSC6H4C(O)OHꢀ)-
SC6H4COOH)]ꢀ (6) IR (THF, cmꢀ1): n(CO) 2010
/
/
/
(ꢀ
/
(vs), 1920 (s), 1912 (s) [4]. The subsequent elimination of
HSC6H4COOH and the concomitant dimerization of
[Mn(CO)3(ꢀ
/
SC6H4C(O)Oꢀ
/
)]ꢀ fragment yielded the di-
nuclear complex 4. This result revealed that oxidative
addition across the Sꢀ
/
S bond of (SC6H4COOH)2 to
[Mn(CO)5]ꢀ is the preferred pathway of the reaction of
2,2?-dithiosalicylic acid and [Mn(CO)5]ꢀ.
The X-ray structural analysis (Fig. 2) of complex 8
a
Recent results suggested that [Mn(CO)5]ꢀ promoted
the oxidative addition of diorganyl disulfide to yield six-
coordinate cis-[Mn(CO)4(SR)2]ꢀ [15], although cleavage
reveals
centrosymmetric trinuclear manganeseꢂ
/
of Sꢀ
/
S bond by nucleophiles is a well-known phenom-
enon which results in displacement of the group RSꢀ
[16]. In addition, recent work also indicated that the
complexes cis-[Mn(CO)4(ER)2]ꢀ (Eꢁ
yl, alkyl) which contain the delocalized lone pairs of
/
Te, Se; Rꢁphen-
/
electrons around chalcogen atoms are useful in the
syntheses of heterometallic Mn(I)ꢀ
/
Co(III)ꢀ
/
Mn(I)ꢀ
/
chalcogenolate complexes such as [(CO)4Mn(m-
TePh)2Co(CO)(m-TePh)3Mn(CO)3] possessing a unique
CoIII
ꢀCO bond [2a], and [(CO)3Mn(m-SePh)3Co(m-
/
SePh)3Mn(CO)3]ꢀ possessing a homoleptic hexaseleno-
latocobalt(III) core [9]. To evaluate the influence of the
weaker electron-donating thiolate ligand on the stability
of the heterometallic Mn(I)ꢀ
olate complexes, we surveyed the reactivity of bis(o-
benzamidophenyl) disulfide towards Co(ClO4)2×6H2O
/
Co(III)ꢀ
/
Mn(I)ꢀ
/
chalcogen-
/
Scheme 4.

W.-F. Liaw et al. / Inorganica Chimica Acta 332 (2002) 153ꢂ
/159
157
Fig. 2. ORTEP drawing and labeling scheme of [(CO)3Mn(m-SC6H4NHCOPh)3Co(m-SC6H4NHCOPh)3Mn(CO)3]ꢀ with thermal ellipsoids drawn at
the 30% probability level.
cobaltꢂ
/
manganeseꢂ
/
thiolate complex in which the CoIII
nium chloride (Lancaster/Aldrich) were used as
received. Infrared spectra were recorded in a spectro-
meter (Bio-Rad FTS-185) with sealed solution cells (0.1
mm) and KBr windows. NMR spectra were recorded in
a Bruker AC 200 spectrometer, 1H chemical shifts being
relative to tetramethylsilane. A GBC Cintra 10 spectro-
is in a distorted octahedral arrangement with the sulfur
atoms of thiolate in two parallel faces of the octahedron
capped by tricarbonylmanganese(I) fragments. The
structure of complex 8 contains two independent
molecules of 8. The Mnꢀ
the staggered conformation of two parallel triangular
thiolate faces promise the best minimization of interac-
/
CoꢀMn angle of 180.08 and
/
photometer was used to record UVꢂVis spectra. Cyclic
/
voltammetric measurements were performed in a BAS-
100B electrochemical analyzer, using glassy carbon as
the working electrode. Cyclic voltammograms were
obtained from 2 mM analyte concentration in CH3CN
using 0.1 M [n-Bu4N][PF6] as supporting electrolyte.
Magnetic susceptibilities were carried out in the tem-
tions between the thiolates. The Sꢀ S angles are
divided into two groups (Table 2), 82.16(5) (same facial
/
Coꢀ
/
groups) and 97.84(5)8 (different facial groups). The
CoIII
ꢀ
/
S and MnIꢀ
/
S bond distances are 2.289(1) and
2.375(2) A (average), respectively. The MnIꢀ ꢀ ꢀCoIII
distance (3.1111(9) A) is not short enough to suggest a
bonding interaction between the two metals.
perature range 300ꢂ5 K on a Quantum Design MPMS-
/
5S SQUID magnetometer. Magnetic data were cor-
rected for diamagnetic contribution. Analyses of car-
bon, hydrogen and nitrogen were obtained with a CHN
analyzer (Heraeus).
3. Experimental
Manipulations, reactions, and transfers of samples
were conducted under nitrogen according to standard
Schlenk techniques or in a glove-box (argon gas).
Solvents were distilled under nitrogen from appropriate
drying agents (diethyl ether from CaH2; acetonitrile
3.1. Preparation of [PPN][Mn(ꢀ
/
SC5H4NOꢀ
/
)3] (1)
2,2?-Dithiobis(pyridine N-oxide) (0.8 mmol, 0.202 g)
and [PPN][Mn(CO)5] (0.4 mmol, 0.298 g) were mixed
together in THF solution [19], and stirred at ambient
temperature for 5 min. The reaction was monitored
immediately by IR. IR spectrum (CH3CN, cmꢀ1):
n(CO) 2128 (w) 2043 (sh), 2036 (vs), 2005 (m), and
2020 (vs), 1937 (s), 1920 (s) was assigned to the
from CaH2ꢀ
/
P2O5; methylene chloride from P2O5; hex-
ane and tetrahydrofuran (THF) from sodium-benzo-
˚
phenone) and stored in dried, N2-filled flasks over 4 A
molecular sieves. Nitrogen was purged into these
solvents before use and transferred to reaction vessels
via stainless-steel cannula under a positive pressure of
N2. The reagents dimanganese decacarbonyl, 2,2?-
dithiobis(pyridine N-oxide), 2,2?-dithiosalicylic acid,
bis-(o-benzamidophenyl) disulfide, 1-hydroxy-2-pyridi-
nethione, and bis(triphenylphosphoranylidene)ammo-
formation of cis-[Mn(CO)4(ꢀ
[PPN][Mn(CO)3(ꢀSC5H4NOꢀ)(ꢀ
ally. The mixture was then stirred under airꢂ
/
SC5H4NO)2]ꢀ and fac-
SC5H4NO)] individu-
O2 over-
/
/
/
/
night at r.t. The orange solution was then removed via
cannula, and the yellow precipitate was washed with
THF. Acetonitrile was added to extract the yellow solid,

158
W.-F. Liaw et al. / Inorganica Chimica Acta 332 (2002) 153ꢂ159
/
and then diethyl ether was slowly added to precipitate
the product [PPN][Mn(ꢀSC5H4NOꢀ)3] (1) (yield: 0.233
g, 60%) [10]. The crystals, suitable for X-ray crystal-
lography, were obtained by vapor diffusion of diethyl
ether into a concentrated CH3CN solution of complex 1
then dried under vacuum. The dark green pure complex
8 can be obtained after being separated from the
/
/
CH3CNꢂ
g, 52%). Recrystallization by vapor diffusion of hexaneꢂ
diethyl ether into THF solution at ꢀ15 8C afforded
/diethyl ether-soluble complex 9 (yield 0.467
/
/
at ꢀ
/
15 8C. Absorption spectrum: lmax (nm) (o,
dark green crystals of complex 8 suitable for X-ray
crystallography. IR (THF, cmꢀ1): n(CO) 2008 (vs),
Mꢀ1 cmꢀ1) (CH2Cl2): 345 (7787), 304 (2362), 300
(35 535), 294 (33 696). The effective magnetic moment
in solid state by SQUID magnetometer was 5.88 mB [10].
Anal. Found: C, 62.96; H, 4.41; N, 5.82. Calc. for
C51H42O3P2N4S3Mn: C, 63.02; H, 4.36; N, 5.76%.
1929 (br,s); 1681 (Cꢁ
/
O); 1515 (Nꢀ
/
H). 1H NMR
(C4D8O, d ppm): 6.89 (t), 7.35 (t), 8.24 (d), 8.51 (d)
(SC6H4NH); 3.85 (br) (NH). Absorption spectrum: lmax
(nm) (o, Mꢀ1 cmꢀ1) (THF): 595 (5049), 374 (14 560),
324 (26 964), 314 (36 388). Anal. Found: C, 63.96; H,
4.41; N, 4.92. Calc. for C120H90O12P2N7S6Mn2Co: C,
64.06; H, 3.97; N, 4.39%.
3.2. Preparation of [Et4N]2[(CO)3Mn(m-SC6H4ꢀ
C(O)ꢀOꢀ)2Mn(CO)3] (4)
/
/
/
THF solution (6 ml) containing [Et4N][Mn(CO)5] (0.4
mmol, 0.130 g) [19] and 2,2?-dithiosalicylic acid (0.4
mmol, 0.123 g) was stirred for 4 h at r.t. The reaction
was monitored by IR. IR spectra (THF, cmꢀ1): n(CO)
2073 (w), 2000 (vs), 1979 (m), 1939 (m) (major) and
2010 (vs), 1920 (s), 1912 (s) (minor) were assigned to
4. Crystallography
Crystallographic data of complexes 1 and 8 are
summarized in Table 1, and in the supporting informa-
tion. The crystals of 1 and 8 are chunky. The crystals of
1 and 8 chosen for X-ray diffraction studies measured
the formation of cis-[Mn(CO)4(ꢀ
and SC6H4ꢀC(O)OHꢀ
fac-[Mn(CO)3(ꢀ
C(O)OH)]ꢀ, respectively. After 12 h of stirring the
known orange product [Et4N]2[(CO)3Mn(m-SC6H4ꢀ
C(O)ꢀOꢀ)2Mn(CO)3] (4) [14], as identified by X-ray
/
SC6H4ꢀ
/
C(O)OH)2]ꢀ
)(ꢀSC6H4ꢀ
/
/
/
/
/
0.50ꢄ
/
0.40ꢄ
/
0.06 mm and 0.20ꢄ
/
0.20ꢄ0.10 mm, re-
/
/
spectively. Each crystal was mounted on a glass fiber.
Diffraction measurements for complex 1 was carried out
on a Nonius CAD4 (complex 8 on a Nonius Kappa
CCD) diffractometer with graphite-monochromated
/
/
diffraction and IR, precipitated upon addition of diethyl
ether. Recrystallization from saturated CH3CN solution
with diethyl ether diffusion gave orange crystals of
˚
Mo Ka radiation (l 0.7107 A) and u between 1.75
complex 4 at ꢀ
/
15 8C (yield: 0.143 g, 62%). IR
and 25.008 for complex 1, between 1.49 and 25.008 for
complex 8. Least-squares refinement of the positional
and anisotropic thermal parameters for all non-hydro-
gen atoms and fixed hydrogen atoms contribution was
based on F2. The SHELXTL package of programs was
employed for structure solution and refinement [20].
(CH3CN, cmꢀ1): n(CO) 1997(s), 1900 (vs); 1595 (Cꢁ
/
O).
Caution: perchlorate salts of metal complexes with
organic ligands are potentially explosive; only small
amounts of material should be prepared and handled
with great caution.
3.3. Preparation of [PPN][(CO)3Mn(m-SR)3Co(m-
SR)3Mn(CO)3] (Rꢁ
/
C6H4NHCOPh) (8)
5. Supplementary material
A
solution containing 0.596
g
(0.8 mmol) of
[PPN][Mn(CO)5] and 0.752 g (0.8 mmol) of bis-(o-
benzamidophenyl)disulfide in THF (4 ml) was stirred
at ambient temperature for 15 min. IR spectra, n(CO)
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC Nos. 180392 and 180393 for
compounds 1 and 8, respectively. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2
2061 (w), 1985 (vs), 1966 (m), 1924 (m), 1670 (m) (Cꢁ
1574 (w) (Nꢀ
H) (THF, cmꢀ1) were assigned to the
SC6H4NHCOPh)2]ꢀ [15].
/
O),
/
formation of cis-[Mn(CO)4(ꢀ
/
To the same flask a THF solution of 0.2 mmol of bis-(o-
benzamidophenyl) disulfide (0.188 g) and 0.4 mmol of
1EZ, UK (fax: ꢃ44-1223-336-033; e-mail: depos-
/
it@ccdc.cam.ac.uk or www: http://www.ccdc.cam.a-
c.uk).
Co(ClO4)2×/6H2O (0.107 g) were added slowly and
stirred at r.t. overnight. The IR spectra, n(CO) 2008
(vs), 1929 (s,br) (major) and 2001 (vs), 1922 (s,br)
(minor) (THF, cmꢀ1) indicated the formation of
[(CO)3Mn(m-SR)3Co(m-SR)3Mn(CO)3]ꢀ
(Rꢁ/C6H4-
Acknowledgements
NHCOPh) (8) and the known [(CO)3Mn(m-
SR)3Mn(CO)3]ꢀ (9) individually [17,18]. The dark green
solution was filtered to remove the insoluble solid, and
We thank the National Science Council (Taiwan) for
support of this work.

W.-F. Liaw et al. / Inorganica Chimica Acta 332 (2002) 153ꢂ
/159
159
[11] (a) W.-F. Liaw, C.-H. Chen, G.-H. Lee, S.-M. Peng, Organome-
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