Synthesis and characterization of new thioether derivatives of [Os3(CO)12] and [H2Os3(CO)10]; Crystal and molecular structures of [Os3(CO)11(L)] [Et2S, Pr2S

Journal of Organometallic Chemistry 623 (2001) 191–201

www.elsevier.nl/locate/jorganchem

Synthesis and characterization of new thioether derivatives of

[Os₃(CO)₁₂] and [H₂Os₃(CO)₁₀]; crystal and molecular structures of

[Os₃(CO)₁₁(L)] [Et₂S, Pr₂S, S(CH₂)₅] and

[Os₃(CO)₉(m-H)(m-X){SMe(Bu^t)}] (X=H, OH)

Nitsa K. Kiriakidou-Kazemifar ^a, Eike Kretzschmar ^a,1, Ha˚kan Carlsson ^a,

Magda Monari ^b, Simona Selva ^b, Ebbe Nordlander ^a,*

^aInorganic Chemistry 1, Chemical Center, Lund Uni6ersity, Box 124, S-22100 Lund, Sweden

^bDipartimento di Chimica G. Ciamician, Uni6ersita` degli Studi di Bologna, 6ia Selmi 2, I-40126 Bologna, Italy

Received 20 November 2000; accepted 16 December 2000

Abstract

n

Reaction of [Os₃(CO)₁₁(NCMe)] with R₂S (R=Et, Pr) and MeSBu^tresults in the formation of [Os₃(CO)₁₁(L)] (L=thioether)

clusters in which the thioethers are coordinated in an equatorial site of the triosmium framework. Such monosubstituted clusters

are also formed when [Os₃(CO)₁₀(NCMe)₂] is reacted with R₂S (R=Et, ⁿPr) while reaction of the same cluster with Ph₂S or

MeSPh results in the formation of orthometallated clusters, viz. [Os₃(m-H)(CO)₁₀(m-h²-C₆H₄SR)] and [Os₃(m-H)(CO)₉(m₃-

C₆H₄SPh)]. The similar reaction of [Os₃(m-H)₂(CO)₁₀] with Pr₂S, MeSBu^t, MeSPh or Ph₂S does not lead to discernable products

except when carried out in the presence of trimethylamine N-oxide, which leads to clusters of the general formula [Os₃(CO)₉(m-

H)₂(thioether)]. The crystal and molecular structures of [Os₃(CO)₁₁(L)] (L=Et₂S, Pr₂S, S(CH₂)₅) and [Os₃(CO)₉(m-H)(m-

Keywords: Osmium; Cluster; Thioether; Hydrodesulfurization; Crystal structure

ruthenium, osmium, rhodium and iridium are of special

interest since these metals, and especially their sulﬁdes,

are known to be good HDS catalysts [1], although the

lower cost of molybdenum, and the possibility of pro-

moting the catalytic performance of MoS₂by the addi-

tion of cobalt or nickel, make molybdenum

sulﬁde-based catalysts the choice for industrial HDS

catalysis. Our interest in establishing whether the coor-

dination modes of thioethers can be correlated to elec-

tronic and/or steric factors, and whether the thioether

coordination mode inﬂuences the reactivity of the clus-

ter prompted us to study the coordination of thioethers

to polynuclear metal complexes.

Previous studies of reactions of thioethers with tetra-

hedral ruthenium-, cobalt-, and rhodium-containing

clusters [6,7] and [Rh₆(CO)₁₆] [8] have demonstrated

several bonding modes for thioether ligands. Terminal

coordination, bridging ligands in butterﬂy clusters, and

bridging ligands connecting two clusters have been

1. Introduction

Several models/mechanisms for catalytic hydrodesul-

furization (HDS) reactions have been proposed [1]. The

initial coordination of the organosulfur substrates to

the catalyst surface and the mechanistic details of the

catalytic process(es) are not completely understood,

although models for the interaction of thiols and

thioethers with metal surfaces and subsequent desulfur-

ization reactions have been presented [2]. In order to

model possible reaction intermediates in HDS pro-

cesses, we are currently undertaking a broad study of

the interactions of sulfur-containing molecules with

transition metal clusters [3–5]. Clusters containing

* Corresponding author. Tel.: +46-46-2228118; fax: +46-46-

2224439.

E-mail address: ebbe.nordlander@inorg.lu.se (E. Nordlander).

¹Present address: Fachhochschule Ansbach, Residenzstr. 8, DE-

91522 Ansbach, Germany.

PII: S0022-328X(01)00643-X

192

N.K. Kiriakidou-Kazemifar et al. / Journal of Organometallic Chemistry 623 (2001) 191–201

observed. Similarly, Adams and coworkers have shown

that thioethers may coordinate to trinuclear clusters in

monodentate as well as bridging didentate coordination

modes [18,19]. Reactions of alkyl and aryl sulﬁdes with

[M₃(CO)₁₂] (M=Ru, Os) afforded the clusters [Os₃(m-

H)(m-SR)(m₃-h²-C₆H₄)(CO)₉] (R=Me, ⁱPr) [9] and

[Ru₃(m-SPh)(m-h¹;h⁶-C₆H₅)(CO)₈] [10] as a result of

aryl-S cleavage. Furthermore, Adams and coworkers

[11,12] have studied the coordination chemistry of

strained ring thioethers such as thiirane and thietane

with polynuclear metal carbonyl clusters; the release of

ring strain in these cyclic thioethers should lead to more

facile CꢀS bond cleavage processes. Thiiranes undergo

facile elimination of sulfur to yield the corresponding

oleﬁn. Metal atoms promote the desulfurization, and

through this reaction these molecules have been found

to serve as clean sources of monoatomic sulfur for use

in the synthesis of polynuclear metal complexes con-

taining sulﬁdo ligands. Unlike thiiranes, thietanes can

serve as effective ligands in metal complexes through

the coordination of one or both of the lone pairs of

electrons on the sulfur atom, which has resulted in

complexes containing both terminally coordinated and

bridging ligands between two metal atoms [13–16].

UV–vis irradiation/photolysis of [Os₃(CO)₁₁{S(CH₂)₃}]

[17] or the dimethyl homologue [Os₃(CO)₁₁-

(SCH₂CMe₂CH₂)] [14] has been shown to lead to ring-

opening and formation of clusters containing thiametal-

lacyclic rings. A facile ring-opening transformation of

tetrahydrothiophene by a triosmium cluster complex

has also been reported [18]; both CꢀH and CꢀS cleav-

age were observed.

Here, we wish to report the reactions of a number of

thioethers with [Os₃(CO)_12−n(NCMe)_n] (n=1,2) and

[Os₃(m-H)₂(CO)₁₀], which have led to the isolation of

several new clusters of general formulae [Os₃(CO)₁₁(L)]

and [Os₃(m-H)₂(CO)₉(L)] (L=thioether). When aryl

sulﬁdes were used as ligands, triosmium clusters con-

taining orthometallated phenyl substituents could be

isolated.

2. Results and discussion

2.1. Reaction of [Os₃(CO)₁₁(NCMe)] with R₂S (R=Et,

ⁿPr) and MeSBu^t

In order to prepare clusters with thioethers in

monodentate coordination modes, 1–1.5 equivalents of

an appropriate thioether ligand L was added to a

dichloromethane solution of [Os₃(CO)₁₁(NCMe)] at

room temperature, leading to the formation of

[Os₃(CO)₁₁(L)] [L=Et₂S (1), Pr₂S (2), MeSBu^t(3)] in

moderate to good yields (20–60%). In addition, the

previously reported cluster [Os₃(CO)₁₁{S(CH₂)₅}] (4)

[19], containing the cyclic pentamethylene sulﬁde lig-

and, was isolated in low yield from the reaction of the

ligand with [Os₃(CO)₁₀(NCMe)₂] (vide infra). The prod-

1

ucts were identiﬁed by IR and H-NMR spectroscopy

as well as mass spectrometry. Comparison of the w_CꢀO

IR stretching patterns of 1–4 to those of known clus-

ters [19] indicated that the thioethers were in all cases

coordinated in equatorial positions on the trinuclear

cluster framework.

Fig. 1. An ORTEP plot of the molecular structure of [Os₃(CO)₁₁(SEt₂)]

1, showing the atom labelling scheme. Thermal ellipsoids are drawn

at the 30% probability level.

2.2. Crystal and molecular structures of [Os₃(CO)₁₁(L)]

[L=Et₂S (1), Pr₂S (2), S(CH₂)₅(4)]

It was possible to grow yellow crystals of 1, 2, and 4

by slow evaporation of dichloromethane–hexane solu-

tions at 4°C; in order to conﬁrm the equatorial coordi-

nation of the thioethers in these clusters, their

molecular structures were determined by X-ray diffrac-

tion. The molecular structures of compounds 1, 2 and 4

are illustrated in Figs. 1–3 and selected bond lengths

and angles are listed in Tables 1–3. In each compound,

the osmium atoms form an irregular triangle with all

three OsꢀOs distances being inequivalent, and the

Fig. 2. An ^ORTEPplot of the molecular structure of [Os₃(CO)₁₁(SPr₂)]

2, showing the atom labelling scheme. Thermal ellipsoids are drawn

at the 30% probability level.

N.K. Kiriakidou-Kazemifar et al. / Journal of Organometallic Chemistry 623 (2001) 191–201

193

thioether ligand is coordinated via the sulfur atom at an

equatorial coordination site of one Os atom. The aver-

,

age OsꢀOs distances [2.868 A (1), 2.860 A (2), 2.872 A

(4)] are slightly shorter than those found in the parent

,

compound, [Os₃(CO)₁₂] [OsꢀOs_ave=2.877(3) A] [20]. A

general trend in metal–metal distances is observed; the

longest OsꢀOs interactions in 1, 2 and 4 [Os(1)ꢀOs(3)

,

2.886(1), 2.881(2) and 2.894(1) A, respectively] are in cis

position with respect to the S atom of the thioether

ligand, presumably in order to alleviate steric crowding.

On the other hand, the shortest OsꢀOs separations

,

[Os(1)ꢀOs(2)=2.841(1), 2.822(2) and 2.847(1) A, re-

spectively] are those trans to the S atoms as the pres-

ence of good | donors causes a contraction of the

MꢀM bond in trans position [21]. The OsꢀS distances

Fig. 3. An ORTEP plot of the molecular structure of

[Os₃(CO)₁₁{S(CH₂)₅}] 5, showing the atom labelling scheme. Thermal

ellipsoids are drawn at the 30% probability level.

,

for 1, 2 and 4 [2.400(4), 2.398(3) and 2.406(4) A,

respectively] are similar to those found in the terminally

coordinated compounds [Os₃(CO)₁₁{S(CH₂)₃}] [17],

[Os₃(CO)₁₀{S(CH₂)₄}₂] [18] and in the complex

[Os₃(CO)₈(m-SCH₂CH₂CH₂CH₂C){S(CH₂)₅}(m-H)₂] [19]

which contains one terminally coordinated pen-

tamethylene sulﬁde ligand and one bridging an OsꢀOs

bond [OsꢀS=2.375(5), 2.404(ave) and 2.396(3) (termi-

Table 1

,

Selected bond lengths (A) and angles (°) for [Os₃(CO)₁₁(SEt₂)] (1)

Bond lengths

Os(1)ꢀOs(2)

Os(1)ꢀOs(3)

Os(2)ꢀOs(3)

Os(1)ꢀS(1)

S(1)ꢀC(12)

S(1)ꢀC(14)

Os(1)ꢀC(1)

C(1)ꢀO(1)

Os(1)ꢀC(2)

C(2)ꢀO(2)

Os(1)ꢀC(3)

C(3)ꢀO(3)

Os(2)ꢀC(4)

C(4)ꢀO(4)

2.841(1)

2.886(1)

2.876(2)

2.400(4)

1.84(2)

1.79(2)

1.91(2)

1.15(2)

1.94(2)

1.14(2)

1.88(2)

1.14(2)

1.98(2)

1.13(3)

Os(2)ꢀC(5)

C(5)ꢀO(5)

Os(2)ꢀC(6)

C(6)ꢀO(6)

Os(2)ꢀC(7)

C(7)ꢀO(7)

Os(3)ꢀC(8)

C(8)ꢀO(8)

Os(3)ꢀC(9)

C(9)ꢀO(9)

Os(3)ꢀC(10)

C(10)ꢀO(10)

Os(3)ꢀC(11)

C(11)ꢀO(11)

1.89(2)

1.18(2)

1.89(2)

1.14(2)

1.96(2)

1.12(2)

1.95(2)

1.14(2)

1.90(2)

1.17(3)

1.94(3)

1.11(3)

1.89(3)

1.14(3)

,

nal) A, respectively]. The pentamethylene sulﬁde ligand

in compound 4 adopts the stable chair conformation as

was also found for the terminal thioether in

[Os₃(CO)₈(m-SCH₂CH₂CH₂CH₂C)(S(CH₂)₅)(m-H)₂] [19].

It is worth noting that in 1 and 4 there is signiﬁcant

tilting of the Os(CO)₄and of the Os(CO)₃(SR₂) groups

with respect to the Os₃plane. This distortion occurs

presumably to reduce the steric interaction between the

thioether ligand and the axial carbonyls that face the

same side of the molecule.

Bond angles

2.3. Reaction of [Os₃(CO)₁₀(NCMe)₂] with Et₂S, Pr₂S,

S(CH₂)₅, MeSPh and SPh₂

Os(2)ꢀOs(1)ꢀOs(3)

C(1)ꢀOs(1)ꢀC(2)

C(1)ꢀOs(1)ꢀC(3)

C(2)ꢀOs(1)ꢀC(3)

S(1)ꢀOs(1)ꢀC(1)

S(1)ꢀOs(1)ꢀC(2)

S(1)ꢀOs(1)ꢀC(3)

S(1)ꢀOs(1)ꢀOs(2)

S(1)ꢀOs(1)ꢀOs(3)

C(1)ꢀOs(1)ꢀOs(2)

C(1)ꢀOs(1)ꢀOs(3)

C(2)ꢀOs(1)ꢀOs(2)

C(2)ꢀOs(1)ꢀOs(3)

60.28(3)

179.1(9)

90.7(8)

88.7(8)

91.0(6)

88.5(6)

105.7(6)

151.52(9)

93.6(1)

96.1(6)

82.7(6)

84.7(6)

98.0(6)

C(5)ꢀOs(2)ꢀOs(1)

C(5)ꢀOs(2)ꢀOs(3)

C(6)ꢀOs(2)ꢀOs(1)

C(6)ꢀOs(2)ꢀOs(3)

C(7)ꢀOs(2)ꢀOs(1)

C(7)ꢀOs(2)ꢀOs(3)

Os(1)ꢀOs(3)ꢀOs(2)

C(8)ꢀOs(3)ꢀC(9)

C(8)ꢀOs(3)ꢀC(10)

C(8)ꢀOs(3)ꢀC(11)

C(9)ꢀOs(3)ꢀC(10)

C(9)ꢀOs(3)ꢀC(11)

C(10)ꢀOs(3)ꢀC(11)

C(8)ꢀOs(3)ꢀOs(1)

C(8)ꢀOs(3)ꢀOs(2)

C(9)ꢀOs(3)ꢀOs(1)

C(9)ꢀOs(3)ꢀOs(2)

C(10)ꢀOs(3)ꢀOs(1)

C(10)ꢀOs(3)ꢀOs(2)

C(11)ꢀOs(3)ꢀOs(1)

C(11)ꢀOs(3)ꢀOs(2)

C(12)ꢀS(1)ꢀC(14)

C(12)ꢀS(1)ꢀOs(1)

C(14)ꢀS(1)ꢀOs(1)

154.9(7)

95.8(7)

99.0(7)

158.6(6)

93.5(6)

84.2(7)

59.09(3)

94.2(9)

173.1(9)

94(1)

It is well established that the reaction of

[Os₃(CO)₁₀(NCMe)₂] with two-electron donors in gen-

eral leads to the formation of disubstituted complexes

[22], but the reaction of [Os₃(CO)₁₀(NCMe)₂] with 3,3-

dimethylthietane is an exception which yields only the

mono-thietane complex [Os₃(CO)₁₀(m-SCH₂CMe₂CH₂)],

in which the ligand is bridging two osmium atoms

through the sulfur [14]. With the aim of preparing

similar clusters with didentate bridging thioethers,

[Os₃(CO)₁₀(NCMe)₂] was reacted with Et₂S, Pr₂S,

S(CH₂)₅, and Ph₂S; however, in no case could the

desired product, [Os₃(CO)₁₀(m-SR₂)], be obtained.

Somewhat surprisingly, the only products that could be

isolated from the reactions of [Os₃(CO)₁₀(NCMe)₂] with

Et₂S or Pr₂S were the monosubstituted clusters 1 and 2

(vide supra) which were identiﬁed by IR spectroscopy

and mass spectrometry. These products must be due to

(relatively complex) disproportionation reactions. Pre-

sumably, these reactions occur via initial formation of

89(1)

102(1)

92(1)

C(3)ꢀOs(1)ꢀOs(2) 101.8(5)

C(3)ꢀOs(1)ꢀOs(3) 159.8(6)

94.1(6)

81.6(5)

99.2(6)

157.2(6)

79.2(8)

93.3(7)

156.7(8)

100.6(9)

102(1)

Os(1)ꢀOs(2)ꢀOs(3)

C(4)ꢀOs(2)ꢀC(5)

C(4)ꢀOs(2)ꢀC(6)

C(4)ꢀOs(2)ꢀC(7)

C(5)ꢀOs(2)ꢀC(6)

C(5)ꢀOs(2)ꢀC(7)

C(6)ꢀOs(2)ꢀC(7)

C(4)ꢀOs(2)ꢀOs(1)

C(4)ꢀOs(2)ꢀOs(3)

60.62(3)

91(1)

88.3(9)

176.8(9)

105.2(9)

92(1)

91(1)

83.5(6)

95.2(5)

111.0(6)

111.4(6)

194

N.K. Kiriakidou-Kazemifar et al. / Journal of Organometallic Chemistry 623 (2001) 191–201

Table 3

[Os₃(CO)₁₀(NCMe)(SR₂)] and subsequent abstraction

of a CO ligand from a second cluster to form the

product. The adventitious presence of [Os₃(CO)₁₁-

(NCMe)] may also be the cause of formation of some

product, but the relatively high yields of the reactions

(50–60%) may not be ascribed to the presence of the

mono-acetonitrile cluster (assuming that any amount of

carbon monoxide may be abstracted from a single

cluster, the theoretical yield for a CO disproportiona-

tion reaction would be 90%).

As has been previously observed by Adams and

coworkers [19], reaction of the cyclic thioether pen-

tamethylene sulﬁde, S(CH₂)₅, with [Os₃(CO)₁₀(NCMe)₂]

resulted in the formation of a bright yellow product

which could be identiﬁed as the disubstituted cluster

[Os₃(CO)₁₀{S(CH₂)₅}₂] 5 on the basis of IR spec-

,

Selected bond lengths (A) and angles (°) for [Os₃(CO)₁₁{S(CH₂)₅}] (4)

Bond lengths

Os(1)ꢀOs(2)

Os(1)ꢀOs(3)

Os(2)ꢀOs(3)

Os(1)ꢀS(1)

S(1)ꢀC(12)

S(1)ꢀC(16)

Os(1)ꢀC(1)

C(1)ꢀO(1)

Os(1)ꢀC(2)

C(2)ꢀO(2)

Os(1)ꢀC(3)

C(3)ꢀO(3)

Os(2)ꢀC(4)

C(4)ꢀO(4)

2.847(1)

2.894(1)

2.876(1)

2.398(3)

1.80(1)

1.92(1)

1.14(1)

1.94(2)

1.14(2)

1.83(2)

1.16(2)

1.92(1)

1.14(1)

Os(2)ꢀC(5)

C(5)ꢀO(5)

Os(2)ꢀC(6)

C(6)ꢀO(6)

Os(2)ꢀC(7)

C(7)ꢀO(7)

Os(3)ꢀC(8)

C(8)ꢀO(8)

Os(3)ꢀC(9)

C(9)ꢀO(9)

Os(3)ꢀC(10)

C(10)ꢀO(10)

Os(3)ꢀC(11)

C(11)ꢀO(11)

1.92(1)

1.15(2)

1.91(2)

1.13(2)

1.88(2)

1.16(2)

1.90(1)

1.14(1)

1.90(1)

1.14(1)

1.89(1)

1.15(2)

1.94(1)

1.14(1)

Bond angles

Os(2)ꢀOs(1)ꢀOs(3)

C(1)ꢀOs(1)ꢀC(2)

C(1)ꢀOs(1)ꢀC(3)

C(2)ꢀOs(1)ꢀC(3)

S(1)ꢀOs(1)ꢀC(1)

S(1)ꢀOs(1)ꢀC(2)

S(1)ꢀOs(1)ꢀC(3)

S(1)ꢀOs(1)ꢀOs(2)

S(1)ꢀOs(1)ꢀOs(3)

C(1)ꢀOs(1)ꢀOs(2)

C(1)ꢀOs(1)ꢀOs(3)

C(2)ꢀOs(1)ꢀOs(2)

C(2)ꢀOs(1)ꢀOs(3)

C(3)ꢀOs(1)ꢀOs(2)

60.14(3)

178.2(5)

89.3(6)

92.5(6)

91.7(4)

87.5(4)

100.7(5)

159.47(8)

100.23(9)

85.6(4)

97.8(4)

94.5(4)

80.7(4)

99.6(5)

C(5)ꢀOs(2)ꢀOs(1)

C(5)ꢀOs(2)ꢀOs(3)

C(6)ꢀOs(2)ꢀOs(1)

C(6)ꢀOs(2)ꢀOs(3)

C(7)ꢀOs(2)ꢀOs(1)

C(7)ꢀOs(2)ꢀOs(3)

Os(1)ꢀOs(3)ꢀOs(2)

C(8)ꢀOs(3)ꢀC(9)

C(8)ꢀOs(3)ꢀC(10)

C(8)ꢀOs(3)ꢀC(11)

C(9)ꢀOs(3)ꢀC(10)

C(9)ꢀOs(3)ꢀC(11)

C(10)ꢀOs(3)ꢀC(11)

C(8)ꢀOs(3)ꢀOs(1)

C(8)ꢀOs(3)ꢀOs(2)

C(9)ꢀOs(3)ꢀOs(1)

C(9)ꢀOs(3)ꢀOs(2)

C(10)ꢀOs(3)ꢀOs(1)

C(10)ꢀOs(3)ꢀOs(2)

C(11)ꢀOs(3)ꢀOs(1)

C(11)ꢀOs(3)ꢀOs(2)

C(12)ꢀS(1)ꢀC(16)

C(12)ꢀS(1)ꢀOs(1)

C(16)ꢀS(1)ꢀOs(1)

85.4(4)

90.9(4)

165.6(4)

105.1(4)

93.0(5)

153.2(5)

59.12(3)

95.4(5)

88.7(5)

174.3(5)

100.9(6)

90.3(5)

89.9(5)

79.1(3)

92.4(3)

152.1(4)

94.2(4)

106.2(4)

164.7(4)

96.0(3)

87.5(4)

97.3(7)

107.1(5)

111.8(4)

Table 2

,

Selected bond lengths (A) and angles (°) for [Os₃(CO)₁₁(SPr₂)] (2)

Bond lengths

Os(1)ꢀOs(2)

Os(1)ꢀOs(3)

Os(2)ꢀOs(3)

Os(1)ꢀS(1)

S(1)ꢀC(12)

S(1)ꢀC(15)

Os(1)ꢀC(1)

C(1)ꢀO(1)

Os(1)ꢀC(2)

C(2)ꢀO(2)

Os(1)ꢀC(3)

C(3)ꢀO(3)

Os(2)ꢀC(4)

C(4)ꢀO(4)

2.822(2)

2.881(2)

2.877(1)

2.406(4)

1.81(1)

1.83(2)

1.88(1)

1.13(1)

1.89(1)

1.22(1)

1.87(1)

1.17(1)

1.90(1)

1.11(1)

Os(2)ꢀC(5)

C(5)ꢀO(5)

Os(2)ꢀC(6)

C(6)ꢀO(6)

Os(2)ꢀC(7)

C(7)ꢀO(7)

Os(3)ꢀC(8)

C(8)ꢀO(8)

Os(3)ꢀC(9)

C(9)ꢀO(9)

Os(3)ꢀC(10)

C(10)ꢀO(10)

Os(3)ꢀC(11)

C(11)ꢀO(11)

1.91(1)

1.16(1)

1.89(2)

1.19(2)

1.89(1)

1.13(1)

1.91(1)

1.17(1)

1.91(1)

1.16(1)

1.89(1)

1.13(2)

1.90(1)

1.13(2)

C(3)ꢀOs(1)ꢀOs(3) 157.6(5)

Os(1)ꢀOs(2)ꢀOs(3)

C(4)ꢀOs(2)ꢀC(5)

C(4)ꢀOs(2)ꢀC(6)

C(4)ꢀOs(2)ꢀC(7)

C(5)ꢀOs(2)ꢀC(6)

C(5)ꢀOs(2)ꢀC(7)

C(6)ꢀOs(2)ꢀC(7)

C(4)ꢀOs(2)ꢀOs(1)

C(4)ꢀOs(2)ꢀOs(3)

60.74(3)

174.5(5)

88.5(6)

92.6(6)

92.7(6)

92.3(6)

101.4(6)

92.1(3)

83.6(3)

Bond angles

Os(2)ꢀOs(1)ꢀOs(3)

C(1)ꢀOs(1)ꢀC(2)

C(1)ꢀOs(1)ꢀC(3)

C(2)ꢀOs(1)ꢀC(3)

S(1)ꢀOs(1)ꢀC(1)

S(1)ꢀOs(1)ꢀC(2)

S(1)ꢀOs(1)ꢀC(3)

S(1)ꢀOs(1)ꢀOs(2)

S(1)ꢀOs(1)ꢀOs(3)

C(1)ꢀOs(1)ꢀOs(2)

60.59(5)

89.7(5)

175.3(5)

102.9(4)

83.2(3)

92.4(2)

157.05(9)

97.2(1)

C(5)ꢀOs(2)ꢀOs(1)

C(5)ꢀOs(2)ꢀOs(3)

C(6)ꢀOs(2)ꢀOs(1)

C(6)ꢀOs(2)ꢀOs(3)

C(7)ꢀOs(2)ꢀOs(1)

C(7)ꢀOs(2)ꢀOs(3)

Os(1)ꢀOs(3)ꢀOs(2)

C(8)ꢀOs(3)ꢀC(9)

C(8)ꢀOs(3)ꢀC(10)

C(8)ꢀOs(3)ꢀC(11)

C(9)ꢀOs(3)ꢀC(10)

C(9)ꢀOs(3)ꢀC(11)

88.4(4)

89.7(3)

90.1(4)

90.6(4)

100.2(5)

160.9(5)

58.69(5)

174.2(6)

87.9(7)

93.9(7)

91.4(6)

91.8(8)

troscopy and mass spectrometry (cf. [19]). A small

amount of [Os₃(CO)₁₁{S(CH₂)₅}] (4) (vide supra) was

also formed. To our knowledge, 5 and the correspond-

ing tetrahydrothiophene cluster [Os₃(CO)₁₀(SC₄H₈)₂]

[18] are the only examples of multiple thioether substi-

tution on a triosmium cluster. The reasons for the

99.0(4)

C(1)ꢀOs(1)ꢀOs(3) 159.5(4)

C(2)ꢀOs(1)ꢀOs(2)

C(2)ꢀOs(1)ꢀOs(3)

C(3)ꢀOs(1)ꢀOs(2)

C(3)ꢀOs(1)ꢀOs(3)

Os(1)ꢀOs(2)ꢀOs(3)

C(4)ꢀOs(2)ꢀC(5)

C(4)ꢀOs(2)ꢀC(6)

C(4)ꢀOs(2)ꢀC(7)

C(5)ꢀOs(2)ꢀC(6)

C(5)ꢀOs(2)ꢀC(7)

C(6)ꢀOs(2)ꢀC(7)

90.3(3)

89.1(3)

94.4(4)

93.1(4)

60.72(5)

90.6(7)

91.3(7)

103.4(7)

178.0(6)

90.0(6)

89.1(6)

C(10)ꢀOs(3)ꢀC(11) 102.4(7)

C(8)ꢀOs(3)ꢀOs(1)

C(8)ꢀOs(3)ꢀOs(2)

C(9)ꢀOs(3)ꢀOs(1)

C(9)ꢀOs(3)ꢀOs(2)

C(10)ꢀOs(3)ꢀOs(1)

C(10)ꢀOs(3)ꢀOs(2)

C(11)ꢀOs(3)ꢀOs(1)

C(11)ꢀOs(3)ꢀOs(2)

C(12)ꢀS(1)ꢀC(15)

C(12)ꢀS(1)ꢀOs(1)

C(15)ꢀS(1)ꢀOs(1)

89.8(4)

88.8(4)

84.8(4)

relative

stabilities

of

[Os₃(CO)₁₀(m-SR₂)]

vs.

[Os₃(CO)₁₀(SR₂)₂] are unclear. In either case, an initial

intermediate, ‘[Os₃(CO)₁₀(SR₂)(NCMe)]’, may be envis-

aged, and the capability of the thioether to act as a

four-electron bridging ligand is likely to determine

which product is formed (Scheme 1). It may thus be

expected that thioethers with good s-donor capabilities

(e.g. SMe₂) will be prone to coordinate in briding

modes.

90.1(3)

103.9(4)

162.3(4)

153.6(6)

95.3(6)

103.7(8)

110.9(6)

108.5(5)

C(4)ꢀOs(2)ꢀOs(1) 156.4(5)

C(4)ꢀOs(2)ꢀOs(3) 95.7(5)

N.K. Kiriakidou-Kazemifar et al. / Journal of Organometallic Chemistry 623 (2001) 191–201

195

Scheme 1. Schematic depiction of reactions of [Os₃(CO)₁₀(NCMe)₂] with thioethers observed in this work and by Adams and coworkers [14,18,19].

Formation of mono-substituted [Os₃(CO)₁₁(thioether)] has also been observed, see text.

Reaction of [Os₃(CO)₁₀(NCMe)₂] with the phenyl

containing ligands SPh₂or MeSPh, under the same

conditions as above, resulted in CꢀH activation and

metallation of the phenyl substituent rather than

thioether coordination on the trinuclear cluster. In the

case of Ph₂S, two products were isolated and identiﬁed.

The ¹H-NMR of the ﬁrst, major, product showed a

resonance at −14.41 ppm, consistent with the presence

of a bridging hydride, and three signals assigned to a

cyclometallated m-C₆H₄moiety were observed at 8.04

(d, 1H), 6.92 (m, 2H) and 6.74 (t, 1H) ppm. The IR

pattern of this product is very similar to the known

[Os₃(CO)₁₀{m-PhSC₂CH₂C(Me)Bu^t}(m-H)] [23] and the

product is therefore proposed to be [Os₃(m-H)(CO)₁₀(m-

h²-C₆H₄SPh)] (6); the mass spectrum of 6 is fully

consistent with this formulation. The second product

was isolated in low yield and identiﬁed as [Os₃(m-

2.4. Treatment of [Os₃(v-H)₂(CO)₁₀] with Pr₂S,

MeSBu^tor Ph₂S in the presence of Me₃NO

It has been shown that reactions between [Os₃(m-

H)₂(CO)₁₀] and tertiary phosphines lead to clusters of

the type [HOs₃(m-H)(CO)₁₀(L)], which can exist in sev-

eral different structural isomers in which the phosphine

is known to coordinate in both axial and equatorial

sites on the trinuclear cluster [24,25]. The sum of the

Taft |* constants for the substituents of thioethers

have been used as estimates of the relative s-donor

strengths of thioethers [26]; in addition, cone angles (q)

for a number of thioethers have been derived [26,27]

and combinations of the two factors have been used to

describe the relative nucleophilicity of thioethers

[26,27]. Although the variations in cone angles and

s-donor strengths for the thioethers used in this study

are relatively small², it is nevertheless possible that these

properties may give rise to different coordination

modes in putative [HOs₃(m-H)(CO)₁₀(RSR%)] clusters. In

an attempt to obtain [HOs₃(m-H)(CO)₁₀(L)] clusters

(L=thioether) and ascertain the coordination modes of

the sulfur ligands in such clusters, [Os₃(m-H)₂(CO)₁₀]

was reacted with one equivalent of SPh₂or MeSBu^tin

dichloromethane at ambient temperature. No reaction

1

H)(CO)₉(m₃-C₆H₄SPh)] (7) on the basis of H-NMR, IR

and mass spectrometry. A hydride signal at −14.85

ppm and resonances at 5.85 (d, 1H), 6.70 (t, 1H), 6.92

1

(t, 1H) and 7.89 (d, 1H) in the H-NMR spectrum of 7

are consistent with an ortho-metallated phenyl moiety.

The w_CꢀOIR stretching pattern is similar to that of the

known [Os₃(CO)₉{m₃-PhSC₂CH₂C(Me)Bu^t}(m-H)] [23]

and the mass spectrum is consistent with the above-

mentioned formulation. Similarly, [Os₃(m-H)(CO)₁₀(m-

h²-SC₆H₄Me)] was the major product observed in the

reaction with MeSPh. The w_CꢀOIR stretching pattern is

identical to that of compound 6 and a hydride peak is

²For the thioethers studied here, the values are Et₂S: q=88°,

|*= −0.20; Pr₂S: q=88°, |*= −0.23; MeSBu^t: q=100°, |*= −

1

observed in the H-NMR at −14.7 ppm. The reactions

t

0.30 (average of values for Me₂S and Bu₂S); S(CH₂)₅: q=82° (based

of [Os₃(CO)₁₀(NCMe)₂] with thioethers may be summa-

rized by Scheme 1.

on the cone angle for 1,4-thioxane, derived from experimental data

[26]); Ph₂S: q=97°, MeSPh: q=88° (data taken from [26,27])

196

N.K. Kiriakidou-Kazemifar et al. / Journal of Organometallic Chemistry 623 (2001) 191–201

Table 4

could be observed after 20 h in either case, and reﬂux of

the reaction mixtures at 40°C for another 4 h resulted

in decomposition.

,

Selected bond lengths (A) and angles (°) for [Os₃(CO)₉(m-

H)₂{SMe(Bu^t)}] (10)

However, treatment of [Os₃(m-H)₂(CO)₁₀] with

equimolar amounts of Me₃NO and an appropriate

thioether (Pr₂S, MeSBu^t, Ph₂S) resulted in a change of

color from purple to red and the formation of new

clusters of the general formula [Os₃(m-H)₂(CO)₉(L)]

[L=Pr₂S (8), Ph₂S (9), MeSBu^t(10)]. Addition of

trimethylamine N-oxide to carbonyl complexes gener-

ates coordinative unsaturation via the oxidation of CO

to CO₂; the coordinative unsaturation may be (lightly)

stabilized by coordination of NMe₃. A possible coordi-

natively unsaturated species formed from [Os₃(m-

H)₂(CO)₁₀] would be ‘[Os₃(m-H)₂(CO)₉]’ which may be

expected to be very electrophilic as it would be a

four-electron deﬁcient 44e⁻cluster; this explains the

ready addition of thioethers which appear to be rela-

tively poor nucleophiles. While the hydrides in [Os₃(m-

H)₂(CO)₁₀] and [HOs₃(m-H)(CO)₁₀(L)] (L=phosphine)

[24,25] are ﬂuxional at ambient temperature, the bridg-

ing hydrides in 8–10 give rise to a signal at approxi-

Bond lengths

Os(1)ꢀOs(2)

Os(1)ꢀOs(3)

Os(2)ꢀOs(3)

S(1)ꢀOs(1)

S(1)ꢀC(10)

S(1)ꢀC(14)

Os(1)ꢀC(1)

C(1)ꢀO(1)

Os(1)ꢀC(2)

C(2)ꢀO(2)

Os(2)ꢀC(3)

C(3)ꢀO(3)

2.683(1)

2.785(1)

2.797(1)

2.418(3)

1.85(1)

1.81(1)

1.86(1)

1.14(1)

1.86(1)

1.13(1)

1.89(1)

1.15(1)

Os(2)ꢀC(4)

C(4)ꢀO(4)

Os(2)ꢀC(5)

C(5)ꢀO(5)

Os(3)ꢀC(6)

C(6)ꢀO(6)

Os(3)ꢀC(7)

C(7)ꢀO(7)

Os(3)ꢀC(8)

C(8)ꢀO(8)

Os(3)ꢀC(9)

C(9)ꢀO(9)

1.92(1)

1.11(1)

1.92(1)

1.12(1)

1.90(1)

1.13(1)

1.91(1)

1.13(2)

1.94(1)

1.14(1)

1.94(1)

1.13(1)

Bond angles

Os(2)ꢀOs(1)ꢀOs(3)

C(1)ꢀOs(1)ꢀC(2)

C(1)ꢀOs(1)ꢀH(1)

C(1)ꢀOs(1)ꢀH(2)

C(1)ꢀOs(1)ꢀS(1)

C(2)ꢀOs(1)ꢀH(1)

C(2)ꢀOs(1)ꢀH(2)

C(2)ꢀOs(1)ꢀS(1)

S(1)ꢀOs(1)ꢀH(1)

S(1)ꢀOs(1)ꢀH(2)

S(1)ꢀOs(1)ꢀOs(2)

S(1)ꢀOs(1)ꢀOs(3)

61.49(3)

88.8(5)

174(3)

94(2)

97.8(4)

98(2)

172(3)

104.2(4)

79(4)

C(5)ꢀOs(2)ꢀH(2)

C(3)ꢀOs(2)ꢀOs(1)

C(3)ꢀOs(2)ꢀOs(3)

C(4)ꢀOs(2)ꢀOs(1)

C(4)ꢀOs(2)ꢀOs(3)

C(5)ꢀOs(2)ꢀOs(1)

C(5)ꢀOs(2)ꢀOs(3)

H(1)ꢀOs(2)ꢀOs(1)

H(1)ꢀOs(2)ꢀOs(3)

H(2)ꢀOs(2)ꢀOs(1)

H(2)ꢀOs(2)ꢀOs(3)

Os(1)ꢀOs(3)ꢀOs(2)

C(6)ꢀOs(3)ꢀC(7)

C(6)ꢀOs(3)ꢀC(8)

C(6)ꢀOs(3)ꢀC(9)

C(7)ꢀOs(3)ꢀC(8)

C(7)ꢀOs(3)ꢀC(9)

C(8)ꢀOs(3)ꢀC(9)

C(6)ꢀOs(3)ꢀOs(1)

C(6)ꢀOs(3)ꢀOs(2)

C(7)ꢀOs(3)ꢀOs(1)

C(7)ꢀOs(3)ꢀOs(2)

C(8)ꢀOs(3)ꢀOs(1)

C(8)ꢀOs(3)ꢀOs(2)

C(9)ꢀOs(3)ꢀOs(1)

C(9)ꢀOs(3)ꢀOs(2)

C(10)ꢀS(1)ꢀC(14)

C(10)ꢀS(1)ꢀOs(1)

C(14)ꢀS(1)ꢀOs(1)

172(3)

127.5(3)

91.7(3)

108.2(3)

169.3(3)

130.1(3)

91.0(3)

43.5(6)

83(3)

1

mately −10 ppm in the H-NMR spectrum for each

83(4)

97.22(7)

158.66(6)

43.5(6)

82(3)

cluster. The IR spectra of 8–10 show similar w(CO)

resonances as known compounds of the type [Os₃(m-

H)₂(CO)₉(L)] (L=PMe₂Ph, PPh₃) [28], and in the case

of 9, the molecular structure has been determined by an

X-ray diffraction study. In the reaction with MeSBu^t, a

minor product was isolated and characterized as

[Os₃(CO)₉(m-H)(m-OH){SMe(Bu^t)}] 11 by X-ray crystal-

lography. The formation of 11 is very likely due to the

adventitious presence of water in the solvent(s) used in

the reaction and/or workup of the crude reaction

product.

57.46(3)

101.2(6)

95.5(5)

91.2(5)

94.2(6)

93.0(5)

169.0(5)

98.7(5)

156.1(5)

160.1(4)

102.6(4)

84.1(4)

84.9(3)

86.3(3)

85.4(3)

102.7(6)

115.8(4)

105.9(4)

C(1)ꢀOs(1)ꢀOs(2) 131.9(3)

C(1)ꢀOs(1)ꢀOs(3) 98.2(4)

C(2)ꢀOs(1)ꢀOs(2) 130.5(4)

C(2)ꢀOs(1)ꢀOs(3)

H(1)ꢀOs(1)ꢀOs(2)

H(1)ꢀOs(1)ꢀOs(3)

H(2)ꢀOs(1)ꢀOs(2)

H(2)ꢀOs(1)ꢀOs(3)

Os(1)ꢀOs(2)ꢀOs(3)

C(3)ꢀOs(2)ꢀC(4)

C(3)ꢀOs(2)ꢀC(5)

C(3)ꢀOs(2)ꢀH(1)

C(3)ꢀOs(2)ꢀH(2)

C(4)ꢀOs(2)ꢀC(5)

C(4)ꢀOs(2)ꢀH(1)

C(4)ꢀOs(2)ꢀH(2)

C(5)ꢀOs(2)ꢀH(1)

90.2(4)

43.8(6)

84(3)

43.6(6)

82(3)

61.05(3)

95.6(4)

90.5(5)

171.0(7)

92(2)

2.5. Crystal and molecular structures of

[Os₃(CO)₉(v-H)₂{SMe(Bu^t)}] 10 and

[Os₃(CO)₉(v-H)(v-OH){SMe(Bu^t)}] 11

96.8(4)

89(4)

90(4)

97(2)

Dark red crystals of [Os₃(CO)₉(m-H)₂){SMe(Bu^t)}] 10

were grown by slow evaporation of a dichloromethane-

hexane solution at 4°C. The molecular structure of 10 is

illustrated in Fig. 4 and selected bond lengths and

angles are listed in Table 4. The molecule consists of a

triangle of osmium atoms where one osmium atom

coordinates to four terminal carbonyls and the remain-

ing two osmium atoms [Os(1) and Os(2)] coordinate to

two and three terminal carbonyls, respectively. The

Os(1)ꢀOs(2) bond is doubly bridged by two hydrides; in

addition, MeSBu^tis terminally coordinated to Os(1) in

an equatorial coordination site. The Os(1)ꢀOs(2) dis-

,

tance [2.683(1) A] is almost identical to that found in

Fig. 4. An ORTEP plot of the molecular structure of [Os₃(CO)₉(m-

H)₂(SMe^tBu)] 10, showing the atom labelling scheme. Thermal ellip-

soids are drawn at the 30% probability level.

,

the parent [Os₃(m-H)₂(CO)₁₀] [2.681(1) A] [29] and

the phosphine-substituted [Os₃(m-H)₂(CO)₉(PPh₃)]

N.K. Kiriakidou-Kazemifar et al. / Journal of Organometallic Chemistry 623 (2001) 191–201

197

Table 5

,

[2.683(2)A] [30] and is very close to that found in

[Os₃(m-H)₂(CO)₉(phosphine)] (phosphine=PMe₂Ph

[28], PⁱPr₃[31], P^tBu₃[32]) where the corresponding

,

Selected bond lengths (A) and angles (°) for [Os₃(CO)₉(m-H)(m-

OH){SMe(Bu^t)}] (11)

,

distances are 2.703(1), 2.689(1) and 2.690(1) A, respec-

tively. This demonstrates that the Os(m-H)₂Os unit is

Bond lengths

Os(1)ꢀOs(2)

Os(1)ꢀOs(3)

Os(2)ꢀOs(3)

O(10)ꢀOs(1)

O(10)ꢀOs(2)

S(1)ꢀOs(1)

S(1)ꢀC(10)

S(1)ꢀC(14)

Os(1)ꢀC(1)

C(1)ꢀO(1)

2.809(1)

2.816(1)

2.832(1)

2.146(7)

2.142(7)

2.438(3)

1.89(1)

1.80(1)

1.89(2)

1.15(2)

1.86(1)

1.12(2)

1.92(2)

C(3)ꢀO(3)

Os(2)ꢀC(4)

C(4)ꢀO(4)

Os(2)ꢀC(5)

C(5)ꢀO(5)

Os(3)ꢀC(6)

C(6)ꢀO(6)

Os(3)ꢀC(7)

C(7)ꢀO(7)

Os(3)ꢀC(8)

C(8)ꢀO(8)

Os(3)ꢀC(9)

C(9)ꢀO(9)

1.14(2)

1.94(1)

1.12(1)

1.88(1)

1.13(1)

1.95(2)

1.12(2)

1.93(2)

1.12(2)

1.93(1)

1.14(2)

1.95(1)

1.13(1)

very little perturbed on ligand substitution. The other

two OsꢀOs bonds are slightly shorter [2.785(1) and

i

,

2.797(1) A] than those found in [Os₃(m-H)₂(CO)₉(P Pr₃)]

,

[2.816(1) and 2.822(1) A] [31] and [Os₃(m-H)₂(CO)₁₀]

,

[2.815 and 2.814 A] [29] and the OsꢀOs bond trans to S

is the shortest, as was also found for 1, 2 and 4 (vide

,

supra). The OsꢀS bond length [2.418(3) A] is slightly

longer than the analogous OsꢀS distances [range 2.38–

Os(1)ꢀC(2)

C(2)ꢀO(2)

Os(2)ꢀC(3)

,

2.40 A] found in the terminally coordinated triosmium

cluster complexes discussed above.

Orange crystals of [Os₃(CO)₉(m-H)(m-OH){SMe-

(Bu^t)}] 11 were grown by slow evaporation of a

dichloromethane solution at room temperature. The

molecular structure of 11 is shown in Fig. 5 and

selected bond lengths and angles are listed in Table 5.

Compound 11 differs from [Os₃(CO)₉(m-H)₂{SMe-

(Bu^t)}] 10 by the presence of a bridging OH group

which replaces one of the two bridging hydrides. As a

result of this substitution, the unsaturated 46e⁻cluster

10 becomes the saturated 48e⁻cluster 11; thus, a direct

comparison of the 46 and 48 electron species can be

undertaken. In addition to the S atom of the thioether,

the oxygen of the bridging hydroxy ligand is a chiral

center as it is coordinated to two non-equivalent Os

atoms and exo or endo conﬁgurations (referring to the

relative position of the hydrogen of the OH moiety to

the osmium triangle [33]) are possible. The m-OH moi-

ety spans the Os(1)ꢀOs(2) bond symmetrically [OsꢀO

Bond angles

Os(2)ꢀOs(1)ꢀOs(3)

C(1)ꢀOs(1)ꢀC(2)

C(1)ꢀOs(1)ꢀH(1)

C(1)ꢀOs(1)ꢀO(10)

C(1)ꢀOs(1)ꢀS(1)

C(2)ꢀOs(1)ꢀH(1)

60.44(2)

88.3(6)

173(3)

98.8(4)

98.0(4)

91(2)

C(5)ꢀOs(2)ꢀO(10)

C(3)ꢀOs(2)ꢀOs(1)

C(3)ꢀOs(2)ꢀOs(3)

C(4)ꢀOs(2)ꢀOs(1)

C(4)ꢀOs(2)ꢀOs(3)

C(5)ꢀOs(2)ꢀOs(1)

C(5)ꢀOs(2)ꢀOs(3)

H(1)ꢀOs(2)ꢀOs(1)

H(1)ꢀOs(2)ꢀOs(3)

O(10)ꢀOs(2)ꢀOs(1)

O(10)ꢀOs(2)ꢀOs(3)

Os(1)ꢀOs(3)ꢀOs(2)

C(6)ꢀOs(3)ꢀC(7)

C(6)ꢀOs(3)ꢀC(8)

C(6)ꢀOs(3)ꢀC(9)

C(7)ꢀOs(3)ꢀC(8)

C(7)ꢀOs(3)ꢀC(9)

C(8)ꢀOs(3)ꢀC(9)

C(6)ꢀOs(3)ꢀOs(1)

C(6)ꢀOs(3)ꢀOs(2)

C(7)ꢀOs(3)ꢀOs(1)

C(7)ꢀOs(3)ꢀOs(2)

C(8)ꢀOs(3)ꢀOs(1)

C(8)ꢀOs(3)ꢀOs(2)

C(9)ꢀOs(3)ꢀOs(1)

C(9)ꢀOs(3)ꢀOs(2)

C(10)ꢀS(1)ꢀC(14)

C(10)ꢀS(1)ꢀOs(1)

C(14)ꢀS(1)ꢀOs(1)

169.5(4)

133.0(4)

87.3(4)

114.7(4)

174.2(4)

120.8(4)

93.7(4)

40.3(6)

81(3)

49.1(2)

83.4(2)

59.66(2)

100.8(6)

91.4(6)

94.7(6)

93.4(6)

94.8(6)

168.7(5)

98.0(4)

157.6(4)

161.2(4)

101.6(4)

86.3(4)

85.3(4)

83.4(4)

85.4(3)

103.1(6)

116.0(4)

106.8(4)

C(2)ꢀOs(1)ꢀO(10) 171.2(4)

C(2)ꢀOs(1)ꢀS(1)

S(1)ꢀOs(1)ꢀH(1)

S(1)ꢀOs(1)ꢀO(10)

S(1)ꢀOs(1)ꢀOs(2)

S(1)ꢀOs(1)ꢀOs(3)

C(1)ꢀOs(1)ꢀOs(2) 136.0(4)

C(1)ꢀOs(1)ꢀOs(3) 91.2(4)

C(2)ꢀOs(1)ꢀOs(2) 122.2(4)

C(2)ꢀOs(1)ꢀOs(3)

H(1)ꢀOs(1)ꢀOs(2)

H(1)ꢀOs(1)ꢀOs(3)

O(10)ꢀOs(1)ꢀOs(2) 49.0(2)

O(10)ꢀOs(1)ꢀOs(3) 83.7(2)

Os(1)ꢀOs(2)ꢀOs(3)

C(3)ꢀOs(2)ꢀC(4)

C(3)ꢀOs(2)ꢀC(5)

C(3)ꢀOs(2)ꢀH(1)

C(3)ꢀOs(2)ꢀO(10)

C(4)ꢀOs(2)ꢀC(5)

C(4)ꢀOs(2)ꢀH(1)

C(4)ꢀOs(2)ꢀO(10)

C(5)ꢀOs(2)ꢀH(1)

99.1(4)

90(3)

85.1(2)

106.32(7)

166.51(7)

91.0(4)

40.3(6)

81(3)

59.90(2)

95.8(5)

91.5(5)

168(3)

98.4(4)

91.1(5)

96(3)

,

2.146(7) and 2.142(7) A]. The doubly bridged

,

Os(1)ꢀOs(2) bond distance of 2.809(1) A is the shortest

of the three metal–metal bonds and strictly comparable

,

to that found in [Os₃(CO)₉(m-H)(m-OH)] [2.806(1) A]

[34]. This can be attributed to the shortening effect of

91.3(4)

88(2)

the bridging hydroxy group prevailing on the lengthen-

ing effect of the bridging hydride. The two remaining

OsꢀOs bonds are longer than the analogous distances in

,

10 [Os(1)ꢀOs(3) 2.816(1) vs. 2.785(1) A and Os(2)ꢀOs(3)

,

2.832(1) vs. 2.797(1) A] as a consequence of the elec-

tronic saturation of the cluster.

3. Conclusions

Fig. 5. An ORTEP plot of the molecular structure [Os₃(CO)₉(m-H)(m-

OH)(SMe^tBu)] 13, showing the atom labelling scheme. Thermal ellip-

soids are drawn at the 30% probability level.

In the present study, reaction of [Os₃(CO)₁₁(NCMe)]

with thioethers leads in all cases examined to the for-

198

N.K. Kiriakidou-Kazemifar et al. / Journal of Organometallic Chemistry 623 (2001) 191–201

4.1. Synthesis of [Os₃(CO)₁₁(SEt₂)] (1)

mation of [Os₃(CO)₁₁(L)] (L=thioether), albeit in mod-

erate yield. The thioethers are coordinated in an equa-

torial site of the triosmium framework and there is no

evidence for other coordination modes. On the other

hand, the outcome of reactions of [Os₃(CO)₁₀(NCMe)₂]

with thioethers is less predictable and the factors gov-

erning product formation in these reactions require

further detailed studies. For some thioethers, we ob-

serve formation of monosubstituted clusters in rela-

tively high yield while other thioethers yield

disubstituted clusters; no examples of clusters of the

type [Os₃(CO)₁₀(m-SR₂)] could be obtained in this inves-

tigation. Thioethers with aryl substituents undergo oxi-

dative addition of a CꢀH bond of an aryl ring when

reacted with [Os₃(CO)₁₀(NCMe)₂] (cf. Scheme 1).

Reaction of (electrophilic) [Os₃(m-H)₂(CO)₁₀] with the

thioethers used in this work did not lead to discernable

products except when trimethylamine N-oxide was

added to the reaction mixture; in this case, clusters of

the type [Os₃(m-H)₂(CO)₉(L)] (L=thioether) were ob-

tained. The fact that the thioethers used in this study do

not add to the electrophilic dihydride cluster indicates

that they are relatively weak nucleophiles. All new

clusters reported here have been isolated in one form

only; with the exception of enantiomeric forms, no

isomers could be detected in solution or the solid state.

While correlations have been made between stereoelec-

tronic parameters (ligand cone angles and/or s-donor

strengths) and reactivity trends in associative substitu-

tion reactions of complexes of late transition metals

[26,27,35], no correlation between these properties and

the observed ligand coordination modes could be ob-

served for the clusters discussed here. Attempts to

achieve carbon-sulfur bond cleavage of the coordinated

thioethers in compounds 1–10 through thermolysis

with or without the presence of hydrogen gas are

currently being undertaken (cf. [36]).

Diethyl sulﬁde (15 ml, 0.14 mmol) was added by

syringe to a solution of [Os₃(CO)₁₁(NCMe)] (100 mg,

0.11 mmol) in CH₂Cl₂(30 ml) and the mixture was

stirred under nitrogen for 3 h at room temperature.

Removal of the solvent under reduced pressure and

TLC workup, using dichloromethane-hexane (3:7 v/v)

as eluent gave [Os₃(CO)₁₁(SEt₂)] 1, yellow, (32 mg,

30%).

Repeating

the

reaction

using

[Os₃(CO)₁₀(NCMe)₂] as starting material and a longer

reaction time (5 h), but otherwise identical reaction

conditions, gave 1 in a higher yield (50 mg, 48%).

[Os₃(CO)₁₁(SEt₂)] 1: IR (cm⁻¹, CH₂Cl₂): w(CO)

2108w, 2054vs, 2036m, 2017s, 1987sh, 1971m. ¹H-NMR

(CDCl₃)

l (ppm): 2.91 (q, SCH₂CH₃), 1.32 (t,

SCH₂CH₃). MS [FAB+, m/z ]: 970 (M⁺), M⁺-ⁿCO

(n=1–11).

4.2. Synthesis of [Os₃(CO)₁₁(SPr₂)] (2)

Di-n-propyl sulﬁde (20 ml, 0.14 mmol) was added by

syringe to a solution of [Os₃(CO)₁₁(NCMe)] (100 mg,

0.11 mmol) in CH₂Cl₂(25 ml) and the mixture was

stirred under nitrogen for 4–5 h at room temperature.

Removal of the solvent under reduced pressure and

TLC puriﬁcation, using dichloromethane-hexane (1:1

v/v) as eluent, gave [Os₃(CO)₁₁(SPr₂)] 2, yellow, (37 mg,

29%). An identical reaction, using [Os₃(CO)₁₀(NCMe)₂]

as starting material, gave a higher yield of 2 (65 mg,

61%).

[Os₃(CO)₁₁(SPr₂)] 2: IR (cm⁻¹, CH₂Cl₂): w(CO) 2108

w, 2054 s, 2034 s, 2017 vs, 1986 w, 1953 sh. H-NMR

(CDCl₃) l (ppm): 2.93 (t, SCH₂CH₂CH₃), 1.7 (m,

SCH₂CH₂CH₃), 1.05 (t, SCH₂CH₂CH₃). MS [FAB+,

m/z ]: 998 (M⁺), (M⁺-ⁿCO) n=1–11.

1

4.3. Synthesis of [Os₃(CO)₁₁{SMe(Bu^t)}] (3)

Methyl tert-butyl sulﬁde (18 ml, 0.14 mmol) was

added by syringe to a solution of [Os₃(CO)₁₁(NCMe)]

(100 mg, 0.11 mmol) in CH₂Cl₂(35 ml) and the mixture

was stirred under nitrogen for 2 h at room temperature.

Removal of the solvent under reduced pressure and

TLC puriﬁcation, using dichloromethane-hexane (1:1

v/v) as eluent, gave [Os₃(CO)₁₁{SMe(Bu^t)}] 3, yellow,

(70 mg, 66%).

4. Experimental

All manipulations were carried out under an inert

atmosphere of nitrogen using standard Schlenck and

vacuum line techniques. The starting materials

[Os₃(CO)₁₂] [37] and [Os₃(m-H)₂(CO)₁₀] [38] were pre-

pared by published methods. Solvents were freshly dis-

tilled from appropriate drying agents. Thin layer

chromatography (TLC) was carried out on commercial

plates precoated with Merck Kieselgel 60 to 0.5 mm

thickness. Infrared spectra were recorded on a Nicolet

Avatar FT-IR spectrometer, ¹H-NMR spectra on a

Varian Unity 300 MHz spectrometer using the solvent

resonance as an internal standard, and FAB MS (3-ni-

trobenzyl alcohol matrix) on a JEOL SX-102 mass

spectrometer.

[Os₃(CO)₁₁{SMe(Bu^t)}] 3: IR (cm⁻¹, CH₂Cl₂): w(CO)

1

2108w, 2054s, 2036m, 2018vs, 1986w, 1955sh. H-NMR

(CDCl₃) l (ppm): 2.64 (s, MeSBu^t), 1.42 (s, MeSBu^t).

MS [FAB+, m/z ]: 984 (M⁺), (M⁺-ⁿCO) n=1–11.

4.4. Reaction of [Os₃(CO)₁₀(NCMe)₂] with S(CH₂)₅

This reaction is closely related to that reported by

Adams et al. [19]. Pentamethylene sulﬁde (25 ml, 0.24

N.K. Kiriakidou-Kazemifar et al. / Journal of Organometallic Chemistry 623 (2001) 191–201

199

mmol) was added by syringe to

a

solution of

were recovered, in order of decreasing R_f: [Os₃(m-H)₂

(CO)₉(SPr₂)] 8, red (34 mg, 31%) and a yellow, as of yet

uncharacterised product (5 mg).

[Os₃(CO)₁₀(NCMe)₂] (100 mg, 0.11 mmol) in

dichloromethane (20 ml) and the mixture was stirred

under nitrogen at room temperature for 1 h. The

solvent was removed under reduced pressure and the

resulting residue was dissolved in a minimum amount

of CH₂Cl₂and applied to TLC plates. TLC using

dichloromethane-hexane (1:1 v/v) as eluent gave two

bands–in order of decreasing R_f, [Os₃(CO)₁₁{S(CH₂)₅}]

4, pale yellow (20 mg, 15%) and [Os₃(CO)₁₀{S(CH₂)₅}₂]

5, yellow (52 mg, 46%). The spectroscopic data for 4

and 5 were identical to those previously reported [19].

[Os₃(m-H)₂(CO)₉(SPr₂)] 8: IR (cm⁻¹, CH₂Cl₂): w(CO)

2093s, 2054vs, 1010vs, 1990sh, 1941m. ¹H-NMR

(CDCl₃) l (ppm): 3.08 (t, SCH₂CH₂CH₃), 1.76 (m,

SCH₂CH₂CH₃), 1.10 (t, SCH₂CH₂CH₃), (−10.0) (s,

Os(m-H)). MS [FAB+, m/z ]: 944 (M⁺).

4.7. Synthesis of [Os₃(v-H)₂(CO)₉(SPh₂)] (9)

In a typical reaction, [Os₃(m-H)₂(CO)₁₀] (100 mg, 0.12

mmol) and diphenyl sulﬁde (25 ml, 0.15 mmol) were

mixed in CH₂Cl₂(30 ml) and one equivalent of Me₃NO

(12 mg, 0.15 mmol) in CH₂Cl₂was added dropwise

with a dropping funnel during one hour, and stirred

under nitrogen at room temperature for 2 h. A color

change from purple to red was observed. The solvent

was removed under reduced pressure and the resulting

residue dissolved in a minimum amount of CH₂Cl₂and

applied to TLC plates. TLC puriﬁcation, using

dichloromethane-hexane (1:4 v/v) as eluent, gave two

bands, in order of decreasing R_f: [Os₃(m-

H)₂(CO)₉(SPh₂)] 9, red (36 mg, 31%) and a yellow

uncharacterized product (5 mg).

4.5. Synthesis of [Os₃(v-H)(CO)₁₀(v-p²-C₆H₄SPh)] (6)

and [Os₃(v-H)(CO)₉(v₃-C₆H₄SPh] (7)

Diphenyl sulﬁde (39 ml, 0.24 mmol) was added by

syringe to a solution of [Os₃(CO)₁₀(NCMe)₂] [100 mg,

0.11 mmol) in dichloromethane and the mixture was

stirred under nitrogen at room temperature for 3 h. The

solvent was removed under reduced pressure and the

resulting residue was dissolved in a minimum amount

of CH₂Cl₂and puriﬁed by TLC plates using

dichloromethane-hexane (1:4 v/v) as eluent. Three

bands were recovered, in order of decreasing R_f: a

yellow, as of yet uncharacterized product (trace),

[Os₃(m-H)(CO)₁₀(m-h²-SC₆H₄Ph)] 6, intense yellow, (46

mg, 41%) and [Os₃(m-H)(CO)₉(m₃-C₆H₄SPh)] 6, yellow

(7 mg, 6.5%).

[Os₃(m-H)₂(CO)₉(SPh₂)] 9: IR [w(CO) cm⁻¹, CH₂Cl₂]:

1

2096s, 2074w, 2058s, 2015s, 1993s, 1980m, 1953m. H-

NMR [l (ppm), CDCl₃) ]: 7.71–7.24 (m, SPh₂), (−9.6)

(s, Os(m-H)). MS [FAB+, m/z ]: 1012 (M⁺).

[Os₃(m-H)(CO)₁₀(m-h²-C₆H₄SPh)] 6: IR (cm⁻¹

,

CH₂Cl₂): w(CO) 2104s, 2064s, 2052s, 2021m, 2010m,

1992m, 1973sh. ¹H-NMR (CDCl₃) l (ppm): 8.04 (d,

1H, JH-H=7.7 Hz), 7.46–7.24 (m, SPh), 6.92 (q, 2H),

6.74 (t, 1H), (−14.41) (s, Os(m-H). MS [FAB+, m/z ]:

1038(M⁺), (M⁺-ⁿCO) n=1–10.

4.8. Treatment of [Os₃(v-H)₂(CO)₁₀] with MeSBu^tand

one equi6alent Me₃NO

A total of 100 mg [Os₃(m-H)₂(CO)₁₀] (0.12 mmol) and

tert-butyl methyl sulﬁde (20 ml, 0.15 mmol) were mixed

in CH₂Cl₂(30 ml) and one equivalent of Me₃NO (12

mg, 0.15 mmol) in CH₂Cl₂was added dropwise with a

dropping funnel for 1 h, and stirred under nitrogen at

room temperature for 4 h. A color change from purple

to red was observed. The solvent was removed under

reduced pressure and the resulting residue dissolved in a

minimum amount of CH₂Cl₂and applied to TLC

plates, using dichloromethane–hexane (3:7 v/v) as elu-

ent. Two bands were recovered: in order of decreasing

R_f, [Os₃(m-H)₂(CO)₉(SMeBu^t)] 10, red, (56 mg, 53%)

[Os₃(m-H)(m-OH)(CO)₉(SMeBu^t)] 11, yellow (16 mg,

15%) and a yellow, as of yet uncharacterized product

(13 mg).

[Os₃(m-H)(CO)₉(m₃-C₆H₄SPh)] 7: IR (cm⁻¹, CH₂Cl₂):

1

w(CO) 2105m, 2076w, 2067s, 2024s. H-NMR (CDCl₃)

l (ppm): 7.89 (d, C₆H₄SPh), 7.71–7.56 (m, C₆H₄SPh),

7.36–7.22 (m, C₆H₄SPh), 6.92 (t, C₆H₄SPh), 6.70 (t,

C₆H₄SPh), 5.85 (d, C₆H₄SPh), (−14.85) (s, Os(m-H)).

MS [FAB+, m/z ]: 1010 (M⁺), (M⁺-ⁿCO) n=1–9.

4.6. Synthesis of [Os₃(v-H)₂(CO)₉(SPr₂)] (8)

In a typical reaction, [Os₃(m-H)₂(CO)₁₀] (100 mg, 0.12

mmol) and dipropyl sulﬁde (22 ml, 0.15 mmol) were

mixed in CH₂Cl₂(30 ml). To this solution, one equiva-

lent of Me₃NO (12 mg, 0.15 mmol) in CH₂Cl₂was

added dropwise with a dropping funnel during one

hour, and the resultant solution was stirred under nitro-

gen at room temperature for another 2 h, during which

time a color change from purple to red was observed.

The solvent was removed under reduced pressure and

the resulting residue was dissolved in a minimum

amount of CH₂Cl₂and puriﬁed by TLC plates, using

dichloromethane-hexane (1:4 v/v) as eluent. Two bands

[Os₃(m-H)₂(CO)₉(SMeBu^t)] 10: IR [w(CO) cm⁻¹

,

CH₂Cl₂]: 2096s, 2057vs, 2015vs, 2004s, 1991s, 1979m,

1

1947m. H-NMR [l (ppm), CDCl₃)]: 2.77 (s, MeSBu^t),

1.48 (s, MeSBu^t), (−10.0) (s, Os(m-H)). MS [FAB+,

m/z ]: 930 (M⁺).

[Os₃(m-H)(m-OH)(CO)₉(SMeBu^t)] 11: IR [w(CO)

cm⁻¹, CH₂Cl₂]: 2099s, 2057vs, 2034vw, 2019s, 2015sh,

2002s, 1980m, 1975m, 1938m. ¹H-NMR [l (ppm),

200

N.K. Kiriakidou-Kazemifar et al. / Journal of Organometallic Chemistry 623 (2001) 191–201

CDCl₃) ]: 2.88 (s, MeSBu^t), 1.49 (s, MeSBu^t), (−12.3)

(s, Os(m-H)). MS [FAB+, m/z ]: 946 (M⁺).

calculated positions (d_CꢀH0.98 and 0.95 A, respec-

,

tively). The ﬁnal reﬁnement on F²proceeded by full-

matrix least-squares calculations (SHELX-93 [41]) using

anisotropic thermal parameters for all the non-hydro-

gen atoms. The methyl and methylene hydrogen atoms

were assigned an isotropic thermal parameters 1.5 times

the U_eqvalues of the carrier carbon atoms. The rela-

tively low quality of the diffraction data for compound

1 was due to the fact that good quality crystals could

not be obtained despite repeated crystallizations by

different techniques.

4.9. X-ray data collection and structure determination

of 1, 2, 4, 10 and 11

Crystal data and other experimental details for all

structures are reported in Table 6. The diffraction

experiments for compounds 1, 2, 4, 10 were carried out

on an Enraf-Nonius CAD4 diffractometer at room

temperature, using graphite-monochromatized Mo–K_a

,

radiation (u=0.71073 A). The unit cells were deter-

The X-ray intensity data for 11 were measured on a

Bruker ^{AXS SMART}2000 diffractometer, equipped with

a CCD detector, using Mo–K_aradiation (u=0.71073

mined by a least-squares ﬁtting procedure using 25

randomly selected strong reﬂections. The diffracted in-

tensities were corrected for Lorentz and polarization

effects. An empirical absorption correction was applied

using the azimuthal scan method [39]. The metal atom

positions were determined by direct methods (^SIR-97

[40]) and all non-hydrogen atoms were located from

Fourier difference syntheses. In compound 10, the two

bridging hydrides were also located in the Fourier map.

The methyl and methylene H atoms were added in

,

A) at room temperature. Cell dimensions and the orien-

tation matrix were initially determined from least-

squares reﬁnement on reﬂections measured in three sets

of 20 exposures collected in three different ꢀ regions

and eventually reﬁned against 3615 reﬂections. A full

sphere of reciprocal space was scanned by 0.3° ꢀ steps

with the detector kept at 5.0 cm from the sample.

Table 6

Crystal data and experimental details for [Os₃(CO)₁₁(SEt₂)] (1); [Os₃(CO)₁₁(SPr₂)] (2); [Os₃(CO)₁₁{S(CH₂)₅}] (4); [Os₃(m-H)₂(CO)₉(SMeBu^t)] (10);

[Os₃(m-H)(m-OH)(CO)₉{SMe(Bu^t)}] (11)

Compound

1

2

4

10

11

Empirical formula

Molecular weight

Temperature (K)

C₁₅H₁₀O₁₁Os₃S₁

968.89

293(2)

C₁₇H₁₄O₁₁Os₃S₁

996.94

293(2)

C₁₆H₁₀O₁₁Os₃S₁

980.90

293(2)

C₁₄H₁₄O₉Os₃S₁

928.91

298(2)

C₁₄H₁₄O₁₀Os₃S₁

944.91

293(2)

,

Wavelength (A)

0.71069

Monoclinic

P2₁/n (No. 14)

8.301(4)

16.323(4)

16.653(7)

90

98.48(3)

90

2232(2)

0.71069

Triclinic

0.71069

Monoclinic

P2₁/c (No. 14)

8.289(3)

9.568(3)

28.336(9)

90

93.98(4)

90

2239(1)

4

0.71069

Monoclinic

P2₁/n (No. 14)

10.207(6)

13.992(6)

15.285(7)

90

91.05(4)

90

2183(2)

0.71073

Monoclinic

C2/c (No. 15)

23.212(2)

8.853(1)

21.318(2)

90

90.488(3)

90

4308.8(6)

8

Crystal symmetry

Space group

(

P1 (No. 2)

,

a (A)

9.538(3)

11.413(9)

12.828(4)

70.15(5)

109.47(3)

108.29(5)

1206(1)

2

,

b (A)

,

c (A)

h (°)

i (°)

k (°)

3

,

Cell volume (A )

Z

4

D_calc(Mg m⁻³

)

2.884

17.182

1728

2.745

15.900

896

2.909

17.126

1752

2.827

17.556

1656

2.865

17.449

3376

v(Mo–K_a) (mm⁻¹

F(000)

)

Crystal size (mm)

q limits (°)

Reﬂections collected

0.15×0.22×0.35

2.60–29.98

6492 (9h, +k,

+l)

0.25×0.28×0.35

2.25–30.17

7361 (9h, 9k,

+l)

0.05×0.12×0.40

2.25–24.98

3450 (9h, +k,

+l)

0.10×0.15×0.25

2.38–25.07

3981 (9h, +k,

+l)

0.25×0.30×0.35

1.75–30.16

28864 (9h, 9k,

9l)

Unique observed reﬂections

[F_o\4|(F_o)]

6492

7070

3379

3831

6454

Goodness-of-ﬁt on F²

R₁(F) ^a, wR₂(F²) ^b

Weighting scheme

1.029

1.056

0.0503, 0.1321

a=0.0762,

1.083

1.066

0.0302, 0.0822

a=0.0592,

0.875

0.0748, 0.1885

a=0.1554,

b=0.0000 ^b

0.0334, 0.0627

a=0.0226,

b=19.3098 ^b

0.0420, 0.0896

a=0.0452,

b=0.0000 ^b

b

b=5.6460

b=3.4393

Largest difference peak and hole

2.357 and −2.123 2.192 and −1.661 0.982 and −0.944 1.348 and −1.290 1.663 and −1.072

−3

,

(e A

)

^aR₁=ꢀꢁꢁF_oꢁ−ꢁF_cꢁ/ꢀꢁF_oꢁ.

^bwR₂=[ꢀw(F²_o−F²_c)²/ꢀw(F²_o)²]^1/2where w=1/[|²(F²_o)+(aP)²+bP] where P=(F_o²+2F²_c)/3.

N.K. Kiriakidou-Kazemifar et al. / Journal of Organometallic Chemistry 623 (2001) 191–201

201

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kanen, J. Organomet. Chem. 419 (1991) 219.

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(1982) 235.

[10] W.R. Cullen, S.J. Rettig, T.C. Zheng, Polyhedron 14 (2000) 2653.

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Chem. Soc. 115 (1993) 8207.

Intensity decay was monitored by recollecting the initial

50 frames at the end of the data collection and analyz-

ing the duplicate reﬂections. The collected frames were

processed for integration by using the program ^SAINT

and an empirical absorption correction was applied

using ^SADABS[42] on the basis of the Laue symmetry of

the reciprocal space. The structure was solved by direct

methods (SIR-97) [40] and subsequent Fourier syntheses

and reﬁned by full-matrix-block least-squares on F²

(SHELXTL) [43] using anisotropic thermal parameters

for all non hydrogen atoms. The bridging hydride was

located in the Fourier map and reﬁned with a ﬁxed

isotropic thermal parameter.

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Organometallics 12 (1993) 4955.

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Organometallics 2 (1983) 144.

[22] A.J. Deeming, S. Donovan-Mtunzi, S.E. Kabir, P.J. Manning, J.

Chem. Soc. Dalton Trans. (1985) 1037.

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[24] S. Aime, R. Gobetto, E. Valls, Inorg. Chim. Acta 275 (1998) 521.

[25] E. Nordlander, B.F.G. Johnson, J. Lewis, P.R. Raithby, J.

Chem. Soc. Dalton Trans. (1996) 3825.

5. Supplementary material

Observed and calculated mass spectra for compounds

1–11 (22 pages). Crystallographic data for the struc-

tural analyses have been deposited with the Cambridge

Crystallographic Data Centre, CCDC No. 152932 for

[Os₃(CO)₁₁(SEt₂)] (1), No. 152933 for [Os₃(CO)₁₁(SPr₂)]

(2), No. 152934 for Os₃(CO)₁₁{S(CH₂)₅} (4), No.

152935 for [Os₃(CO)₉(m-H)₂{SMe(Bu^t)}] (10), and No.

152936 for [Os₃(CO)₉(m-H)(m-OH){SMe(Bu^t)}] (11).

Copies of this information may be obtained from The

Director, CCDC, 12 Union Road, Cambridge, CB2

1EZ, UK (Fax: +44-1223-336033; e-mail: de-

posit@ccdc.cam.ac.uk or www: http://www.ccdc.cam.

ac.uk).

[26] T. Shi, L.I. Elding, Inorg. Chem. 35 (1996) 5941.

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9 (1990) 1399.

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Zuccaro, K. Henrick, Acta Crystallogr. Sect. B B35 (1979) 2210.

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Acknowledgements

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1971.

This research has been supported by grants to E.N.

from the Swedish Natural Science Research Council

(NFR) and the Swedish Engineering Sciences Research

Council (TFR) and by grants from the Consiglio

Nazionale delle Ricerche (CNR), MURST (COFIN98)

and the University of Bologna (‘Funds for Selected

Research Topics’) to M.M.

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B 51 (1995) 42.

[35] L. Chen, A.J. Poe¨, Coord. Chem. Rev. 143 (1995) 265.

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Article Doi

Synthesis and characterization of new thioether derivatives of [Os3(CO)12] and [H2Os3(CO)10]; Crystal and molecular structures of [Os3(CO)11(L)] [Et2S, Pr2S

DOI: 10.1016/S0022-328X(01)00643-X

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