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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)

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S 

/

S Bond-activation of diorganyl disulfide by anionic [Mn(CO)

5

]



:

crystal structures of [Mn

II

( 

/

SC

5

H

4

NO 

/

)

3

]



and [(CO)

3

Mn(m-SR)

3

Co(m-SR)

3

Mn(CO)

3

]



(R 

/

C

6

H

4

NHCOPh)

Wen-Feng Liaw

a,

*, Chung-Hung Hsieh

a

, Shie-Ming Peng

b

, Gene-Hsiang Lee

b

aDepartment of Chemistry, National Changhua University of Education, Changhua 50058, Taiwan, ROC bDepartment of Chemistry and Instrumentation Center, National Taiwan University, Taipei 10764, Taiwan, ROC

Received 1 October 2001; accepted 24 December 2001

Abstract

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 [MnII( /SC5H4NO /)3] (1). The effective magnetic moment in solid state by SQUID

magnetometer was 5.88 mBfor complex 1, which is consistent with the MnIIhaving a high-spin d5electronic 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(m-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(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) /thiolate; S /S Bond-activation; Heterotrinuclear Mn /Co /Mn /thiolate

1. Introduction

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

shown to give rise to an extensive chemistry [2 /8]. Some

known reactions are outlined in Scheme 1: oxidative addition of diorganyl dichalcogenides to [Mn(CO)5]

affording cis -[Mn(CO)4(ER)2] (E /Se, Te; R /

phen-yl, alkyl) (Scheme 1(a)) [2], coordinative addition of [Mn(CO)5] to TeCl4 to form a discrete

chlorotellur-olate [Cl4Te /Mn(CO)5] (Scheme 1(b)) [3], the

six-coordinate MnI complex fac -[Mn(CO)3( /SC5H4N /)( /

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

-( /EC6H4NH /)] (E /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 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

acid /base reaction to yield the five-coordinate

[Mn(CO)3( /SC6H4S /)] 

(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: 886-4-721 1190. E-mail address: chfeng@cc.ncue.edu.tw(W.-F. Liaw).

www.elsevier.com/locate/ica

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

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[Mn(CO)3(DBCat)] (DBCat /3,5-di-t

-butyl-1,2-cate-cholate) (Scheme 1(h)) [8].

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 hexacoordinate MnII complex [Mn( /

SC5H4NO /)3] (1), and [(CO)3Mn(m-SC6H4/C(O) /

O /)2Mn(CO)3]2 (4) are described. In addition, the

synthesis and structure of a linear trinuclear MnI/

CoIII/MnIcomplex possessing a hexathiolatocobalt(III)

core, [(CO)3Mn(m-SR)3Co(m-SR)3Mn(CO)3] (R /

C6H4NHCOPh) (8) is also reported [9]. The variable

valence tris(1-hydroxy-2-pyridinethionato) mangane-se(II,III,IV), characterized by UV /Vis, EPR, and cyclic

voltammogram, were investigated by Chakravorty and coworkers [10].

2. Results and discussion

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( /SC5H4NO /)3](1)

iden-tified by X-ray diffraction analysis. Compound 1 was isolated as the PPN salt and a yellow solid from CH3CN /diethyl 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

-bonded) cis -[Mn(CO)4( /SC5H4NO)2] (2) (Scheme

2(a)) [2]. Chelation of one terminal thiolate ligand of intermediate 2 yields the fac -[Mn(CO)3

-( /SC5H4NO /)( /SC5H4NO)] (3) where one of the

anionic [ /SC5H4NO /] ligands bound to the MnI

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))

[8]. Apparently, the metal-center oxidation (MnI0/

MnII) of intermediate 3, labilizing CO ligands and accompanied by intermetal [ /SC5H4NO /]



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 redox reactions at /0.34 and 0.18 V (vs. Ag /AgNO3),

consistent with the observations by Chakravorty and coworkers [10]. The effective magnetic moment in solid state by SQUID magnetometer was 5.88 mBfor complex

1, which is consistent with the MnIIhaving a high-spin d5electronic 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.

Fig. 1 depicts the structure of complex 1 as anORTEP; significant bond distances and angles are given in Table 2. The constraints of the bidentate 1-oxo-2-pyridi-nethione ligand generate (ca. 76.12(8)8, O(1) /Mn /

S(1); 77.05(7)8, O(2) /Mn /S(2); and 75.06(7)8, O(3) /

Mn /S(3) angles) a severe distortion from octahedron

at the hexacoordinate manganese(II) sites. The three sulfur atoms are generally disposed trans to the oxygen atoms [155.13(9)8, O(1) /Mn /S(3); 162.92(8)8, O(2) /

Mn /S(1); and 159.36(8)8 O(3) /Mn /S(2) angles]. Three

S and three O atoms are in an almost ideal facial

Scheme 1.

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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) /

SPh distance of 2.442(3) A˚ (average) in the [Mn(SPh)4]2 [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 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

observed S /C distance (1.692(4) A˚ , average) in complex

1 which indicates the importance of a conjugated interaction along the ring p-system, the S and O lone-pair electrons, and the average S /C length of 1.692(4) A˚

(average) in complex 1 is in agreement with the thione form (Scheme 2(c)) [13]. The average N /O bond length

of 1.326(4) A˚ is well within the range observed for pyridine 1-oxide [13c], indicating that the negative charge of the bidentate [ /SC5H4NO /] ligand in

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 thiolate-donor [ /SC5H4NO] ligand, while the O ,S

-chelating [ /SC5H4NO /] ligand enhances the stability

of manganese in the higher oxidation state (MnII) (Scheme 2) [13].

Under similar reaction condition, the known dianio-nic dinuclear Mn(I) compound [(CO)3Mn(m-SC6H4/

C(O) /O /)2Mn(CO)3]2(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 shown in Scheme 3(a) /(c). Activation of S /S bond

instead of C(O)O /H bond of (SC6H4COOH)2 by

[Mn(CO)5] led to the formation of cis -[Mn(CO)4

-( /SC6H4/C(O) /OH)2] (5), as evident from the IR

spectra (THF, cm1): 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

Fig. 1. ORTEPdrawing and labeling scheme of [Mn(  SC5H4NO  )3]

with thermal ellipsoids drawn at the 30% probability level.

Table 1

Crystal data and structure refinement parameters for complexes 1 and 8 1 8× 2.25THF Empirical for-mula C51H42O3N4S3P2Mn C129H108O14.25N7S6P2CoMn2 Formula weight 971.95 2407.33

Crystal system monoclinic rhombohedral

Temperature (K)

295 (2) 150 (1)

l(A˚ ) (Mo Ka) 0.7107 0.7107

Space group P 21/n R 3c

Unit cell dimensions

a (A˚ ) 10.320(2) 32.2239(2) b (A˚ ) 23.333(4) 32.2239(2) c (A˚ ) 19.526(4) 76.5564(7) a (8) 90 90 b (8) 94.593(15) 90 g (8) 90 120 V (A˚3) 4686.9(14) 68 844.3(9) Z 4 24 Dcalc(g cm3) 1.377 1.394 m(cm1) 5.31 5.65 Ra 0.0406 0.0667 RWF2 b 0.0801 0.1873 Goodness-of-fit 1.021 1.058 a R  aj(jFojjFcj)/ajFoj. b RWF 2  {a[w (Fo 2 Fc 2 )2]/a[w (Fo 2 )2]}1/2. Table 2

Selected bond distances (A˚ ) and bond angles (8) for complexes 1 and 8 Complex 1 Bond distances Mn  O(3) 2.127(3) Mn  O(2) 2.172(2) Mn  O(1) 2.156(3) Mn  S(1) 2.5619(12) Mn  S(2) 2.5331(14) Mn  S(3) 2.6485(13) S(1)  C(1) 1.687(4) S(2)  C(6) 1.686(4) S(3)  C(11) 1.704(4) O(1) N(1) 1.325(4) O(2)  N(2) 1.334(4) O(3) N(3) 1.318(3) Bond angles

O(3)  Mn  O(1) 90.44(11) O(3) Mn  O(2) 85.63(10) O(1)  Mn  O(2) 89.88(10) O(3) Mn  S(2) 159.36(8) O(3)  Mn  S(1) 103.94(8) O(3) Mn  S(3) 75.06(7) S(1)  Mn  S(3) 87.72(4) S(2)  Mn  S(1) 95.69(4) S(2)  Mn  S(3) 99.74(4) N(1)  O(1)  Mn 123.8(2) C(1)  S(1)  Mn 98.28(14) Complex 8 Bond distances

Co(1)  S(1) 2.277(1) Co(1)  S(2A) 2.292(1)

Co(1)  S(3) 2.299(2) Mn(1)  S(1) 2.373(2)

Mn(1)  S(2A) 2.367(2) Mn(1)  S(3) 2.386(2)

Bond angles

S(1)  Co(1)  S(1A) 180.00(5) S(3)  Co(1)  S(2) 98.21(5) S(3)  Co(1)  S(1) 82.94(5) S(2)  Co(1)  S(1) 98.26(4) S(3)  Mn(1)  S(1) 79.12(5) S(2A)  Mn(1)  S(3) 78.44(5) S(2A)  Mn(1)  S(1) 78.21(5) Co(1)  S(1)  Mn(1) 83.96(4)

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ligand resulting from chelate formation of one terminal thiolate ligand MnI/SC6H4COOH of complex 5 yielded

the intermediate fac -[Mn(CO)3( /SC6H4C(O)OH /

)-( /SC6H4COOH)] (6) IR (THF, cm1): n (CO) 2010

(vs), 1920 (s), 1912 (s) [4]. The subsequent elimination of HSC6H4COOH and the concomitant dimerization of

[Mn(CO)3( /SC6H4C(O)O /)]fragment yielded the

di-nuclear complex 4. This result revealed that oxidative addition across the S /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] 

. 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

of S /S bond by nucleophiles is a well-known

phenom-enon which results in displacement of the group RS [16]. In addition, recent work also indicated that the complexes cis -[Mn(CO)4(ER)2](E /Te, Se; R /

phen-yl, alkyl) which contain the delocalized lone pairs of electrons around chalcogen atoms are useful in the syntheses of heterometallic Mn(I) /Co(III) /Mn(I) /

chalcogenolate complexes such as [(CO)4

Mn(m-TePh)2Co(CO)(m-TePh)3Mn(CO)3] possessing a unique

CoIII/CO bond [2a], and [(CO)3Mn(m-SePh)3

Co(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) /Co(III) /Mn(I) /

chalcogenolate complexes, we surveyed the reactivity of bis(o -benzamidophenyl) disulfide towards Co(ClO4)2×/6H2O

in the presence of cis -[Mn(CO)4(SR)2] (R /

C6H4NHCOPh). Reaction of (RS)2, Co(ClO4)2×/6H2O

and cis -[Mn(CO)4(SR)2] (R /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)4

Mn(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)3

Mn(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 THF /hexane after being separated

from the CH3CN /diethyl 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, cm1): 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 C3vsymmetry. The1H NMR spectra of complex

8 shows the expected signals for the phenyl groups involved and display characteristics of diamagnetic d6 Co(III) and d6Mn(I) species.

The X-ray structural analysis (Fig. 2) of complex 8 reveals a centrosymmetric trinuclear manganese /

Scheme 3.

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cobalt /manganese /thiolate complex in which the CoIII

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 Mn /Co /Mn angle of 180.08 and

the staggered conformation of two parallel triangular thiolate faces promise the best minimization of interac-tions between the thiolates. The S /Co /S angles are

divided into two groups (Table 2), 82.16(5) (same facial groups) and 97.84(5)8 (different facial groups). The CoIII/S and Mn

I

/S bond distances are 2.289(1) and

2.375(2) A˚ (average), respectively. The MnI  CoIII distance (3.1111(9) A˚) is not short enough to suggest a bonding interaction between the two metals.

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

from CaH2/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-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-photometer was used to record UV /Vis 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-perature range 300 /5 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).

3.1. Preparation of [PPN][Mn( /SC5H4NO /)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, cm1):

n(CO) 2128 (w) 2043 (sh), 2036 (vs), 2005 (m), and 2020 (vs), 1937 (s), 1920 (s) was assigned to the formation of cis -[Mn(CO)4( /SC5H4NO)2] and fac

-[PPN][Mn(CO)3( /SC5H4NO /)( /SC5H4NO)]

individu-ally. The mixture was then stirred under air /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,

Fig. 2. ORTEPdrawing and labeling scheme of [(CO)3Mn(m-SC6H4NHCOPh)3Co(m-SC6H4NHCOPh)3Mn(CO)3]with thermal ellipsoids drawn at

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and then diethyl ether was slowly added to precipitate the product [PPN][Mn( /SC5H4NO /)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

at /15 8C. Absorption spectrum: lmax (nm) (o ,

M1cm1) (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%.

3.2. Preparation of [Et4N]2[(CO)3Mn(m-SC6H4/

C(O) /O /)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, cm1): n (CO) 2073 (w), 2000 (vs), 1979 (m), 1939 (m) (major) and 2010 (vs), 1920 (s), 1912 (s) (minor) were assigned to the formation of cis -[Mn(CO)4( /SC6H4/C(O)OH)2]

and fac -[Mn(CO)3( /SC6H4/C(O)OH /)( /SC6H4/

C(O)OH)], respectively. After 12 h of stirring the known orange product [Et4N]2[(CO)3Mn(m-SC6H4/

C(O) /O /)2Mn(CO)3] (4) [14], as identified by X-ray

diffraction and IR, precipitated upon addition of diethyl ether. Recrystallization from saturated CH3CN solution

with diethyl ether diffusion gave orange crystals of complex 4 at /15 8C (yield: 0.143 g, 62%). IR

(CH3CN, cm1): n(CO) 1997(s), 1900 (vs); 1595 (C /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)3

Co(m-SR)3Mn(CO)3] (R /C6H4NHCOPh) (8)

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) 2061 (w), 1985 (vs), 1966 (m), 1924 (m), 1670 (m) (C /O),

1574 (w) (N /H) (THF, cm 1

) were assigned to the formation of cis -[Mn(CO)4( /SC6H4NHCOPh)2] [15].

To the same flask a THF solution of 0.2 mmol of bis(o -benzamidophenyl) disulfide (0.188 g) and 0.4 mmol of 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, cm1) indicated the formation of [(CO)3Mn(m-SR)3Co(m-SR)3Mn(CO)3] (R /C6H4

-NHCOPh) (8) and the known [(CO)3

Mn(m-SR)3Mn(CO)3](9) individually [17,18]. The dark green

solution was filtered to remove the insoluble solid, and

then dried under vacuum. The dark green pure complex 8 can be obtained after being separated from the CH3CN /diethyl ether-soluble complex 9 (yield 0.467

g, 52%). Recrystallization by vapor diffusion of hexane /

diethyl ether into THF solution at /15 8C afforded

dark green crystals of complex 8 suitable for X-ray crystallography. IR (THF, cm1): n (CO) 2008 (vs), 1929 (br,s); 1681 (C /O); 1515 (N /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 , M1cm1) (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%.

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 0.50 /0.40 /0.06 mm and 0.20 /0.20 /0.10 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 Mo Ka radiation (l 0.7107 A˚ ) and u between 1.75 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 hydronon-hydro-gen atoms contribution was based on F2. The SHELXTL package of programs was employed for structure solution and refinement [20].

5. Supplementary material

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 1EZ, UK (fax: /44-1223-336-033; e-mail:

depos-it@ccdc.cam.ac.uk or www: http://www.ccdc.cam.a-c.uk).

Acknowledgements

We thank the National Science Council (Taiwan) for support of this work.

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References

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(1998) 6396.

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數據

Fig. 1 depicts the structure of complex 1 as an ORTEP ; significant bond distances and angles are given in Table 2
Fig. 1. ORTEP drawing and labeling scheme of [Mn(  SC 5 H 4 NO  ) 3 ]  with thermal ellipsoids drawn at the 30% probability level.
Fig. 2. ORTEP drawing and labeling scheme of [(CO) 3 Mn(m-SC 6 H 4 NHCOPh) 3 Co(m-SC 6 H 4 NHCOPh) 3 Mn(CO) 3 ]  with thermal ellipsoids drawn at the 30% probability level.

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