Synthesis of Arenethiolate Complexes of Divalent and Trivalent Lanthanides from Metallic Lanthanides and Diaryl Bisulfides: Crystal Structures of [{Yb(hmpa)3}2(μ-SPh)3][SPh] and Ln(SPh)3(hmpa)3 (Ln = Sm, Yb; hmpa = Hexamethylphosphoric Triamide)

Article abstract of DOI:10.1021/ic950050i

A convenient and one-pot synthetic method of lanthanide thiolate compounds was developed. An excess of metallic samarium, europium, and ytterbium directly reacted with diaryl disulfides in THF to give selectively Ln(II) thiolate complexes, [Ln(SAr)(μ-SAr)(thf)₃]₂ (1, Ln = Sm; 2, Ln = Eu; Ar = 2,4,6-triisopropylphenyl), Yb(SAr)₂(py)₄ (3, py = pyridine), and [{Ln(hmpa)₃}₂(μ-SPh)3][SPh] (6, Ln = Sm; 7, Ln = Eu; 8, Ln = Yb; hmpa = hexamethylphosphoric triamide). Reaction of metallic lanthanides with 3 equiv of disulfides afforded Ln(III) thiolate complexes, Ln(SAr)₃(py)_n(thf)_3-n (9a, Ln = Sm, n = 3; 9b, Ln = Sm, n = 2; 10, Ln = Yb, n = 3) and Ln(SPh)₃(hmpa)₃ (11, Ln = Sm; 12, Ln = Eu; 13, Ln = Yb). Thus, Ln(II) and Ln(III) thiolate complexes were prepared from the same source by controlling the stoichiometry of the reactants. X-ray analysis of 8 revealed that 8 has the first ionic structure composed of triply bridged dinuclear cation and benezenethiolate anion [8, orthorhombic, space group P2₁2₁2₁ with a = 21.057(9), b = 25.963(7), c = 16.442(8) A?, V = 8988(5) A?³, Z = 4, R -0.040, R_w = 0.039 for 5848 reflections with I > 3σ (I) and 865 parameters]. The monomeric structures of 11 and 13 were revealed by X-ray crystallographic studies [11, triclinic, space group P1? with a = 14.719(3), b = 17.989(2), c = 11.344(2) A?, α = 97.91(1), β= 110.30(2), γ = 78.40(1)°, V = 2751.9(9) A?³, Z = 2, R = 0.045, R_w = 0.041 for 7111 reflections with I > 3σ(I) and 536 parameters; 13, triclinic, space group P1? with a = 14.565(2), b = 17.961(2), c = 11.302(1) A?, α = 97.72(1), β= 110.49(1), γ = 78.37(1)°, V = 2706.0(7) A?³, Z=2, R = 0.031, R_w = 0.035 for 9837 reflections with I > 3σ (7) and 536 parameters]. A comparison with the reported mononuclear and dinuclear lanthanide thiolate complexes has been made to indicate that the Ln-S bonds weakened by the coordination of HMPA to lanthanide metals have ionic character.

Full text of DOI:10.1021/ic950050i

Inorg. Chem. 1996, 35, 93-99
93
Synthesis of Arenethiolate Complexes of Divalent and Trivalent Lanthanides from Metallic
Lanthanides and Diaryl Disulfides: Crystal Structures of [{Yb(hmpa)3}2(µ-SPh)3][SPh] and
Ln(SPh)3(hmpa)3 (Ln ) Sm, Yb; hmpa ) Hexamethylphosphoric Triamide)
Kazushi Mashima,*,† Yuushou Nakayama,‡ Tetsuya Shibahara,‡ Hiroki Fukumoto,† and
Akira Nakamura*,‡,§
Department of Chemistry, Faculty of Engineering Science, Osaka University, Toyonaka,
Osaka 560, Japan, and Department of Macromolecular Science, Faculty of Science,
Osaka University, Toyonaka, Osaka 560, Japan
ReceiVed January 18, 1995X
A convenient and one-pot synthetic method of lanthanide thiolate compounds was developed. An excess of
metallic samarium, europium, and ytterbium directly reacted with diaryl disulfides in THF to give selectively
Ln(II) thiolate complexes, [Ln(SAr)(µ-SAr)(thf)3]2 (1, Ln ) Sm; 2, Ln ) Eu; Ar ) 2,4,6-triisopropylphenyl),
Yb(SAr)2(py)4 (3, py ) pyridine), and [{Ln(hmpa)3}2(µ-SPh)3][SPh] (6, Ln ) Sm; 7, Ln ) Eu; 8, Ln ) Yb;
hmpa ) hexamethylphosphoric triamide). Reaction of metallic lanthanides with 3 equiv of disulfides afforded
Ln(III) thiolate complexes, Ln(SAr)3(py)n(thf)3-n (9a, Ln ) Sm, n ) 3; 9b, Ln ) Sm, n ) 2; 10, Ln ) Yb, n )
3) and Ln(SPh)3(hmpa)3 (11, Ln ) Sm; 12, Ln ) Eu; 13, Ln ) Yb). Thus, Ln(II) and Ln(III) thiolate complexes
were prepared from the same source by controlling the stoichiometry of the reactants. X-ray analysis of 8 revealed
that 8 has the first ionic structure composed of triply bridged dinuclear cation and benezenethiolate anion [8,
orthorhombic, space group P212121 with a ) 21.057(9), b ) 25.963(7), c ) 16.442(8) Å, V ) 8988(5) Å3, Z )
4, R ) 0.040, Rw ) 0.039 for 5848 reflections with I > 3σ(I) and 865 parameters]. The monomeric structures
of 11 and 13 were revealed by X-ray crystallographic studies [11, triclinic, space group P1h with a ) 14.719(3),
b ) 17.989(2), c ) 11.344(2) Å, R ) 97.91(1), â ) 110.30(2), γ ) 78.40(1)°, V ) 2751.9(9) Å3, Z ) 2, R )
0.045, Rw ) 0.041 for 7111 reflections with I > 3σ(I) and 536 parameters; 13, triclinic, space group P1h with a
) 14.565(2), b ) 17.961(2), c ) 11.302(1) Å, R ) 97.72(1), â ) 110.49(1), γ ) 78.37(1)°, V ) 2706.0(7) Å3,
Z ) 2, R ) 0.031, Rw ) 0.035 for 9837 reflections with I > 3σ(I) and 536 parameters]. A comparison with the
reported mononuclear and dinuclear lanthanide thiolate complexes has been made to indicate that the Ln-S
bonds weakened by the coordination of HMPA to lanthanide metals have ionic character.
Introduction
valent organosamarium or ytterbium complexes with organic
disulfides9-11 have been applied. Lanthanide compounds such
as halide,12-15 alkoxide,16-18 amide,19 and organolanthanide
compounds20-27 have been directly prepared from metallic
lanthanides and this is the most effective synthetic strategy. Here
we describe the details of the selective formation of divalent
Lanthanide metals are highly electropositive elements and
have rather high reactivities in general. We are concerned with
the synthesis of lanthanide thiolate compounds from metallic
lanthanides since these compounds have attracted current interest
in the field of organic synthesis1 and as rational molecular
precursors to materials.2 These compounds have been synthe-
sized by the reaction of lanthanide halides with alkali salts of
thiolates.3-5 In these preparations, the rather strong interaction
of lanthanide cations with the alkali-metal halides sometimes
renders the isolation and purification of the products difficult.
To avoid this difficulty, the reaction of alkyl or amido lanthanide
complexes with thiols6-8 and the oxidative reaction of low-
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† Faculty of Engineering Science, Osaka University.
‡ Faculty of Science, Osaka University.
§ 1993-1994, Coordination Chemistry Laboratories, Institute for Mo-
lecular Science, Okazaki National Institutes, Okazaki 444, Japan.
X Abstract published in AdVance ACS Abstracts, November 15, 1995.
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0020-1669/96/1335-0093$12.00/0 © 1996 American Chemical Society

94 Inorganic Chemistry, Vol. 35, No. 1, 1996
Mashima et al.
and trivalent samarium, europium, and ytterbium arenethiolate
complexes by the direct reaction of lanthanide metals with diaryl
disulfides, some details of which have been communicated.28
Results and Discussion
Synthesis of Bis(thiolato)lanthanide(II). The binuclear bis-
(2,4,6-triisopropylbenzenethiolate) complexes of samarium(II)
and europium(II), [Ln(SAr)(µ-SAr)(thf)3]2 (1, Ln ) Sm; 2, Ln
) Eu; SAr ) 2,4,6-triisopropylbenezenethiolate), were prepared
by a direct reaction between a 2-fold excess of metallic
lanthanide and bis(2,4,6-triisopropylphenyl) disulfide in THF
in the presence of a catalytic amount (ca. 3 mol %) of iodine
(eq 1). This reaction did not proceed at all without iodine. The
lanthanide metal was quantitatively consumed within 24 h at
50 °C. Dimeric structures bearing bridging thiolate and terminal
thiolate ligands for 1 and 2 have been revealed by the
crystallographic study.28 In the case of dialkyl disulfide such
as di(tert-butyl) disulfide or dimethyl disulfide, no reaction was
observed under the same conditions. Once isolated as crystals,
complexes 1 and 2 gradually became opaque due to the loss of
THF ligands, resulting in the formation of [Ln(SAr)2(thf)n]2 (Ln
) Sm, n ) 1; Ln ) Eu, n ) 2), based on elemental analyses.
The similar reaction of metallic Yb with bis(2,4,6-triisopropy-
lphenyl) disulfide in THF gave an orange oily product, from
which black crystals of Yb(SAr)2(py)4 (3) were obtained on the
addition of an excess of pyridine to the solution (eq 2).
Recently, Brennan et al. reported the preparation of Yb(SPh)2-
(py)4 (4) by the reaction of diphenyl disulfide with the solvated
Yb metal ion in liquid ammonia or Yb/Hg amalgam in THF,2
and Nief et al. reported the preparation of [Yb(µ-SPh)(η5-C4-
Me4P)(thf)2]2 (5) from metallic Yb and C4Me4PSPh in THF.29
Figure 1. ORTEP drawing of cationic and anionic parts of 8 with a
numbering scheme; 20% probability ellipsoids.
supernatant solution gave the HMPA adduct of ytterbium(II)
complex, [{Yb(hmpa)3}2(µ-SPh)3][SPh] (8), as dark red crystals
(eq 3). Samarium (6) and europium (7) derivatives were also
prepared similarly. The structure of 6-8 was assumed to be
the cationic dimer structure, which was based on the X-ray
analysis of 8 (Vide infra).
In the case of the preparation of 6, the reaction of excess
samarium metal and diphenyl disulfide was carried out in the
presence of HMPA to afford the product together with a
contamination of the tris(benzenethiolate) complex Sm(SPh)3-
(hmpa)3. Thus, the yield of the Sm(II) thiolate complex is
lowered by the coordination of HMPA on samarium, forming
a mononuclear Sm(III) complex. This is consistent with the
fact that the addition of HMPA to the solution of LnI2 (Ln )
Sm and Yb) in THF greatly accelerates the electron transfer
reactions.32 All of these complexes are highly sensitive to air
and moisture. Especially, it was difficult to purify 6 and 7,
resulting in poor elemental analysis data.
I2
Ln (excess) + ArSSAr
8 1/2[Ln(SAr)(µ-SAr)(thf)3]2
THF
1: Ln ) Sm
2: Ln ) Eu
Ar ) 2,4,6-triisopropylphenyl (1)
Yb (excess) + ArSSAr i) I /THF 8 Yb(SAr)2(py)4 (2)
2
ii) py/THF
i) I2/THF
3
Ln (excess) + PhSSPh
8
ii) HMPA/THF
When diphenyl disulfide was used instead of the bulky
substituted diaryl disulfide, the isolation of the product from
the unreacted metal was hampered by the low solubility. This
was solved by the use of HMPA as a ligand. This point has
been noted in the case where uranium thiolates were dissolved
by using HMPA.30,31 The reaction of excess ytterbium metal
with diphenyl disulfide under the same condition as eq 1
afforded a suspension of a sparingly soluble red powder, which
dissolved upon successive addition of 4 equiv of HMPA to the
suspension to give a dark red solution. Removal of the
unreacted metal followed by concentration and cooling of the
1/2[{Ln(hmpa)3}2(µ-SPh)3][SPh] (3)
6: Ln ) Sm
7: Ln ) Eu
8: Ln ) Yb
Molecular Structures of [{Yb(hmpa)3}2(µ-SPh)3][SPh] (8).
The molecular structure of 8 is shown in Figure 1, and the
selected bond distances and angles are listed in Table 1. A
single-crystal X-ray analysis of 8 revealed that complex 8 has
the ionic structure composed of triply bridged dinuclear cation
and benezenethiolate anion, i.e., [{Yb(hmpa)3}2(µ-SPh)3][SPh],
in sharp contrast to the neutral dimer structure found for 1 and
2.28 There is no significant contact between cationic and anionic
molecules. To our knowledge, this is the first example of the
cationic thiolate complexs of lanthanide element together with
thiolate as a counteranion.
In the cationic part of complex 8, each ytterbium metal has
distorted octahedral geometry coordinated by three HMPA
ligands and three bridging benzenethiolate ligands in facial
fashion. Such triply bridged structures are common for thiolate
complexes of transition metals.33,34 Each phenyl plane is nearly
(23) Chauvin, Y.; Olivier, H.; Saussine, L. Inorg. Chim. Acta. 1989, 161,
45.
(24) Hou, Z.; Fujiwara, J.; Jintoku, T.; Mine, N.; Yokoo, K.; Taniguchi,
H. J. Org. Chem. 1987, 52, 3524.
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Org. Chem. 1988, 53, 6077.
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11169.
(27) Mashima, K.; Nakayama, Y.; Nakamura, A.; Kanehisa, N.; Kai, Y.;
Takaya, H. J. Organomet. Chem. 1994, 473, 85.
(28) Mashima, K.; Nakayama, Y.; Fukumoto, H.; Kanehisa, N.; Kai, Y.;
Nakamura, A. J. Chem. Soc., Chem. Commun. 1994, 2523.
(29) Nief, F.; Ricard, L. J. Chem. Soc., Chem. Commun. 1994, 2723.
(30) Leverd, Pascal C.; Lance, Monique; Vigner, Julien; Nierlich, Martine;
Ephritikhine, Michel J. Chem. Soc., Dalton Trans. 1995, 237.
(31) Leverd, P. C.; Arliguie, T.; Ephritikhine, M.; Nierlich, M.; Lance,
M.; Vigner, J. New. J. Chem. 1993, 17, 769.
(32) Handa, Y.; Inanaga, J.; Yamaguchi, M. J. Chem. Soc., Chem. Commun.
1989, 298.
(33) Blower, P. J.; Dilworth, J. R. Coord. Chem. ReV. 1987, 76, 121-185.
(34) Dilworth, J. R.; Hu, J. AdV. Inorg. Chem. 1993, 40, 411.

Arenethiolate Complexes of Lanthanides
Inorganic Chemistry, Vol. 35, No. 1, 1996 95
Table 1. Selected Bond Distances (Å) and Angles (deg) of 8
Bond Distances
Yb(1)-S(1)
Yb(1)-S(2)
Yb(1)-S(3)
Yb(1)-O(1)
Yb(1)-O(2)
Yb(1)-O(3)
S(1)-C(1)
2.902(4)
2.916(4)
2.936(3)
2.351(8)
2.344(9)
2.343(10)
1.74(2)
Yb(2)-S(1)
Yb(2)-S(2)
Yb(2)-S(3)
Yb(2)-O(4)
Yb(2)-O(5)
Yb(2)-O(6)
S(2)-C(7)
2.897(4)
2.930(4)
2.922(4)
2.319(10)
2.320(8)
2.319(9)
1.75(1)
S(3)-C(13)
1.78(2)
S(4)-C(19)
1.75(2)
Bond Angles
S(1)-Yb(1)-S(2)
S(1)-Yb(1)-S(3)
S(2)-Yb(1)-S(3)
78.3(1)
78.8(1)
77.5(1)
S(1)-Yb(2)-S(2)
S(1)-Yb(2)-S(3)
S(2)-Yb(2)-S(3)
78.1(1)
79.1(1)
77.52(10)
S(1)-Yb(1)-O(2) 165.8(3)
S(2)-Yb(1)-O(3) 166.6(2)
S(3)-Yb(1)-O(1) 168.3(2)
S(1)-Yb(2)-O(5) 168.2(2)
S(2)-Yb(2)-O(4) 165.8(3)
S(3)-Yb(2)-O(6) 168.8(3)
Yb(1)-S(1)-C(1)
Yb(1)-S(2)-C(7)
117.9(5)
117.7(7)
Yb(2)-S(1)-C(1)
Yb(2)-S(2)-C(7)
117.9(5)
122.2(6)
Figure 2. ORTEP drawing of 11 with a numbering scheme; 20%
probability ellipsoids. The solvated THF molecule and all hydrogen
atoms are omitted for clarify.
Yb(1)-S(3)-C(13) 116.4(5)
Yb(1)-O(1)-P(1) 171.3(6)
Yb(1)-O(2)-P(2) 170.2(7)
Yb(1)-O(3)-P(3) 167.5(7)
Yb(2)-S(3)-C(13) 115.6(5)
Yb(2)-O(4)-P(4) 169.6(7)
Yb(2)-O(5)-P(5) 172.7(6)
Yb(2)-O(6)-P(6) 167.9(7)
treatment with pyridine. Although this reaction must also occur
at the initial stage of the reaction for the preparation of 1 in eq
1, 1 could be isolated in good yield. This suggests that the
samarium(III) thiolates might be reduced to samarium(II) by
metallic samarium in the condition without HMPA. These tris-
(triisopropylbenezenethiolate) complexes 9a, 9b, and 10 are air-
and moisture-sensitive and easily lose thf and pyridine ligands,
resulting in the poor elemental analysis. The reaction of metallic
europium did not give tris(thiolate) complexes but afforded
complex 2. The smaller negative value of the oxidation potential
of Eu than Sm and Yb is consistent with the above finding.
Yb(1)-S(1)-Yb(2) 87.13(10) Yb(1)-S(2)-Yb(2) 86.25(9)
Yb(1)-S(3)-Yb(2) 86.02(8)
perpendicular to the Yb1-Yb2 vector. The bridging Yb-S
distances (av 2.917(4) Å) are 0.1 Å longer than those of [Yb-
(µ-SPh)(η5-C4Me4P)(thf)2]2 (5) (av 2.817(3) Å).29 On the other
hand, Yb-O(hmpa) distances (av 2.334(9) Å) of 8 are in the
range of those previously reported for other divalent ytterbium
complexes, e.g., [Yb(µ-OCPh2)(hmpa)2]2 [2.28(3) Å],35 Yb-
(OC6H2But2-2,6-Me-4)2(hmpa)2 [2.298(7) Å],35 Yb[µ-OC{Mo-
(CO)2(C5H5)}]2(hmpa)4 [2.33(1) Å],36 and [Yb(hmpa)4(thf)2]I2
[2.357(6) Å].37 The strong coordination of polar HMPA ligands
to the ytterbium metal elongates the Yb-S bonds and this effect
might result in the heterolysis of one Yb-S bond to make the
complex ionic.
Ln + 3/2ArSSAr i) I /THF 8 Ln(SAr)3(py)3
(4)
2
ii) py/THF
9a: Ln ) Sm
10: Ln ) Yb
The Yb-S-C angles of 8 [115.6(5)-122.2(6)°, av 118.0-
(6)°] are in the range of those reported for other 6-coordinated
ytterbium(II) thiolates.2,6 The sums of angles around S(1)
[322.9°], S(2) [326.6°], and S(3) [318.0°] are smaller than 360°,
indicating that the sulfur atoms in 8 are not planar. The Yb-
O-P angles of 8 [167.5(7)-172.7(6)°, av 169.9(7)°] are slightly
larger than those of 6-coordinated ytterbium(III) thiolate (13,
Vide infra).
Synthesis of Tris(thiolato)lanthanide(III). The reaction of
a lanthanide metal powder with 3 equiv of bis(2,4,6-triisopro-
pylphenyl) disulfide in THF in the presence of a catalytic amount
of iodine gave oily compounds, whose formula can be specu-
lated from the final product as Ln(SAr)3(thf)n. Addition of
pyridine to the reaction mixture resulted in the formation of
Ln(SAr)3(py)3 (9a, Ln ) Sm; 10, Ln ) Yb) as orange and red
crystals in 39% and 30% yields, respectively (eq 4). When the
crude crystals of 9a were recrystallized from THF, one of the
pyridine ligands on 9a was replaced by a THF ligand to afford
Sm(SAr)3(py)2(thf) (9b), whose formula was revealed by X-ray
crystallography.28 The reaction of the isolated Sm(II) complex
1 with bis(2,4,6-triisopropylphenyl) disulfide in THF also
resulted in the formation of Sm(III) complex 9a after the
The direct reaction of metallic samarium and diphenyl
disulfide in THF gave an insoluble yellow powder. When the
reaction was carried out in the presence of 3 equiv of HMPA,
Sm(SPh)3(hmpa)3 (11) was obtained as THF-soluble colorless
crystals in 77% yield. Similarly, the europium (12) and
ytterbium (13) derivatives were prepared in moderate yields (eq
5). This is in sharp contrast to the fact that the reaction of
metallic europium with more than 3 equiv of bis(2,4,6-
triisopropylphenyl) disulfide in THF, without HMPA, did not
give europium(III) tris(thiolate). However, this is consistent
with the fact that the addition of HMPA to the solution of LnI2
(Ln ) Sm and Yb) in THF greatly accelerates the electron-
transfer reactions.32 These lanthanide(III) benzenethiolates
bearing HMPA ligands are relatively stable in air compared to
the other lanthanide thiolates reported in this paper, but they
are deliquescent. Elemental analysis of these complexes
indicated that they have one THF as a solvent molecule, which
was further confirmed by crystallographic studies of 11 and 13
(Vide infra). In the case of other lanthanide metals such as lan-
thanum, praseodymium, dysprosium, and neodymium, the rate
of the reaction was much slower than that of Sm, Eu, and Yb.
Ln + 3/2PhSSPh I , HMPA8 Ln(SPh)3(hmpa)3
(5)
2
THF
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(38) Chebolu, V.; Whittle, R. R.; Sen, A. Inorg. Chem. 1985, 24, 3082.
(39) Sen, A.; Chebolu, V.; Rheingold, A. L. Inorg. Chem. 1987, 26, 1821.
(40) Evans, W. J.; Drummond, D. K.; Zhang, H.; Atwood, J. L. Inorg.
Chem. 1988, 27, 575.
11: Ln ) Sm
12: Ln ) Eu
13: Ln ) Yb
Molecular Structures of Sm(SPh)3(hmpa)3 (11) and Yb-
(SPh)3(hmpa)3 (13). The molecular structure of compound 11
is shown in Figure 2 and the selected bond distances and angles

96 Inorganic Chemistry, Vol. 35, No. 1, 1996
Mashima et al.
But2-2,6-Me-4)(hmpa)2 [av 2.333(10) Å],26 and the Yb-
O(hmpa) distances of 13 are comparable to those reported in
YbCl3(hmpa)3 [av 2.224(9) Å]44 and [Yb(H2O)5(hmpa)2]Cl3 [av
2.178(7) Å].44 These Ln-O(hmpa) distances of 11 and 13 are
also comparable to those found in divalent lanthanide complexes
such as SmI2(hmpa)4 [av 2.500(6) Å], [Yb(hmpa)4(thf)2]I2 [av
2.357(6) Å],37 and 8 [av 2.334(9) Å] on taking into account the
difference of ionic radii of Ln2+ and Ln3+ [0.19-0.20 Å for
Sm(II/III) and 0.15-0.16 Å for Yb(II/III)].45
Table 2. Selected Bond Distances (Å) and Angles (deg) in 11 and
13
11
13
Bond Distances
2.815(2)
2.837(2)
2.811(2)
2.307(4)
2.318(4)
2.271(4)
1.756(8)
1.734(7)
1.770(7)
1.495(4)
1.501(4)
1.498(4)
Ln-S(1)
2.740(1)
2.727(1)
2.718(1)
2.181(3)
2.232(2)
2.212(3)
1.752(4)
1.756(4)
1.768(4)
1.492(3)
1.495(2)
1.494(3)
Ln-S(2)
Ln-S(3)
Ln-O(1)
Ln-O(2)
Ln-O(3)
S(1)-C(1)
S(2)-C(7)
S(3)-C(13)
O(1)-P(1)
O(2)-P(2)
O(3)-P(3)
Among the three Yb-S bonds in the complex 13, the bond
distance of Yb-S3 trans to O2 is shorter than those of the other
Yb-S bond cis to O2. Such a tendency has been seen in the
Yb-Cl bonds in the 6-coordinated ytterbium(III) complex
YbCl3(hmpa)3.44 The rather large angles of Ln-O-P (ca. 161-
169°) as well as the observed bond distances of 11 and 13
indicate that the donation of an oxygen atom of HMPA to
lanthanide metal elongates the Ln-S bond cis to HMPA.
For the 6-coordinated trivalent complexes bearing a terminal
thiolate ligand, the Ln-S distances of 9b (2.740(3) Å), 11
(2.821(2) Å), 10 (2.648(6) Å) and 13 (2.728(3) Å) are apparently
shorter than those of divalent complexes such as 1, 2, 4, and
18, indicating that the Ln-S distance is a simple summation of
Bond Angles
162.87(7)
99.87(7)
85.2(1)
S(1)-Ln-S(2)
S(1)-Ln-S(3)
S(1)-Ln-O(1)
S(1)-Ln-O(2)
S(1)-Ln-O(3)
S(2)-Ln-S(3)
S(2)-Ln-O(1)
S(2)-Ln-O(2)
S(2)-Ln-O(3)
S(3)-Ln-O(1)
S(3)-Ln-O(2)
S(3)-Ln-O(3)
O(1)-Ln-O(2)
O(1)-Ln-O(3)
O(2)-Ln-O(3)
Ln-S(1)-C(1)
Ln-S(2)-C(7)
Ln-S(3)-C(13)
Ln-O(1)-P(1)
Ln-O(2)-P(2)
Ln-O(3)-P(3)
164.33(4)
97.42(3)
86.98(7)
80.93(7)
95.41(7)
98.25(4)
91.99(7)
83.42(7)
85.30(7)
93.14(7)
176.85(7)
88.04(7)
89.46(10)
177.18(9)
89.44(10)
117.7(1)
117.2(1)
113.2(1)
169.1(2)
162.3(2)
161.7(2)
83.0(1)
91.2(1)
97.25(6)
95.8(1)
80.0(1)
87.0(1)
88.6(1)
175.8(1)
94.2(1)
88.6(2)
ionic radii of Ln2+ or Ln3+ with that of S2- 45
. As a result,
complexes 11 and 13 are best described by using an ionic bond
model.
Conclusion
175.8(2)
88.8(2)
The synthesis of divalent and trivalent lanthanide arenethiolate
complexes has been achieved by the direct reaction of some
metallic lanthanides with diaryl disulfides. The oxidation states
of the lanthanides in the product can be controlled by the
stoichiometry of the reactants. The X-ray analysis of the
divalent ytterbium thiolate [{Yb(hmpa)3}2(µ-SPh)3][SPh] (8) has
revealed that 8 has ionic structure composed of a triply bridged
dinuclear cation and a benezenethiolate anion. The X-ray
crystallographic studies of tris(benzenethiolate) complexes of
trivalent lanthanides Sm(SPh)3(hmpa)3 (11) and Yb(SPh)3-
(hmpa)3 (13) have revealed their monomeric pseudooctahedral
structure. The elongated Ln-S bond lengths in these complexes
indicate that the coordination of HMPA somewhat weakens the
Ln-S bonds and the ionic nature of these Ln-S bonds are
clearly confirmed.
115.6(3)
116.8(2)
111.5(2)
161.8(3)
162.8(3)
169.2(3)
found in 11 are summarized in Table 2. Compound 13 has
essentially the same structure as 11, and only the selected bond
distances and angles are given in Table 2. Comparative Ln-S
bond distances and Ln-S-C bond angles for these complexes
and the known samarium and ytterbium thiolates are shown in
Table 3.
Both complexes 11 and 13 have essentially the same
mononuclear pseudooctahedral geometry with three benzene
thiolato ligands and three HMPA ligands in meridional fashion
as observed previously for complexes 9b and 10.28 The Ln-S
distances [2.811(2)-2.837(2) Å, av 2.821(2) Å] of 11 are
significantly longer than those found for the other two known
samarium(III) complexes bearing terminal thiolato ligands, e.g.,
Sm(SC6H2But3-2,4,6)3 (14) [2.634(9)-2.652(9) Å, av 2.645(9)
Å]6 and 9b [2.720(3)-2.751(3) Å, av 2.740(3) Å].28 Complex
13 [2.718(1)-2.740(1) Å, av 2.728(3) Å] has the longest Yb-S
bonds among the reported ytterbium(III) complexes bearing
terminal thiolate ligand, e.g., Yb(SPh)(NH3)(η-C5Me5)2 (15)
[2.670(3) and 2.679(3) Å, av 2.675(3) Å]41 and 10 [2.622(7)-
2.665(6) Å; av 2.648(6) Å].28 Thus the coordination of HMPA
to the lanthanide metals elongates the Ln-S bonds and
presumably weakens them, as described for complex 8.
The Sm-O(hmpa) distances of 11 are slightly, but signifi-
cantly, shorter than those reported in the 5-coordinated samari-
Experimental Section
General. All manipulations involving air- and moisture-sensitive
lanthanide compounds were carried out by the use of the standard
Schlenk technique under argon atmosphere. THF and hexane were
dried over sodium benzophenone ketyl and then distilled before use.
1H NMR (270 MHz) spectra were measured on a JEOL GSX-270
spectrometer. Elemental analyses were performed at the Elemental
Analysis Center of Faculty of Science, Osaka University. All melting
points were measured in sealed tubes and were not corrected.
Synthesis of [Sm(SAr)(µ-SAr)(thf)3]2 (1). To samarium metal
powder (453 mg, 3.01 mmol) and bis(2,4,6-triisopropylphenyl) disulfide
(712 mg, 1.51 mmol) in THF (40 mL) was added a catalytic amount
of iodine (12 mg, 0.05 mmol). The reaction mixture was stirred at 50
°C for 24 h. A dark green solution was separated from the unreacted
metal. Concentration of the solution, addition of hexane, and cooling
to -20 °C afforded dark green prisms of 1 (351 mg, 28% yield).
Further concentration and cooling the mother liquor gave second, third,
and fourth crops of crystals. The total yield was 74%. Mp 160-178
°C (dec). Anal. Calcd for C34H54OS2Sm: C, 58.90; H, 7.85. Found:
C, 58.94; H, 8.25.
um(III) complex, Sm{OC(Ph)dCCHdCHCH2CHdCH}2(OC6H2-
(41) Zalkin, A; Henly, T. J.; Andersen, R. A. Acta Crystallogr., Sect. C
1987, 43, 233.
(42) Mashima, K.; Nakayama, Y.; Kanehisa, N.; Kai, Y.; Nakamura, A. J.
Chem. Soc., Chem. Commun. 1993, 1847.
(43) Evans, W. J.; Dominguez, R.; Hanusa, T. P. Organometallics 1986,
5, 263.
(44) Hou, Z.; Kobayashi, K.; Yamazaki, H. Chem. Lett. 1991, 265-268.
(45) Shannon, R. D. Acta Crystallogr. 1976, A32, 751.

Arenethiolate Complexes of Lanthanides
Inorganic Chemistry, Vol. 35, No. 1, 1996 97
Table 3. Comparative Structural Data of Lanthanide Thiolate Complexes
complexesa
d(Ln-S)/Åb
(LnSC)/degb
modec
CNd
6
ref
[Sm(SAr)(µ-SAr)(thf)3]2 (1)
2.908(6)
3.017(6)
2.740(3)
2.821(2)
2.645(9)
2.924(8)
2.883(6)
2.648(6)
2.728(3)
2.675(3)
2.917(4)
2.756(8)
2.817(3)
2.827(3)
124.0(8)
123.7(7)
121.8(3)
114.6(2)
82.9(8)
121.4(7)
127.0(8)
116.8(8)
116.0(1)
118.5(3)
118.0(6)
125.0(8)
terminal
bridging
terminal
terminal
terminal
bridging
bridging
terminal
terminal
terminal
bridging
terminal
bridging
terminal
28
28
Sm(SAr)3(py)2(thf) (9b)
6
6
3
8
7
6
6
8
6
6
7
6
Sm(SPh)3(hmpa)3 (11)
this work
Sm(SC6H2But3-2,4,6)3 (14)
[Sm(µ-SPh)(η-C8H8)(thf)2]2 (16)
[Sm(µ-SAr)(η-C8H8)(thf)]2 (17)
Yb(SAr)3(py)3 (10)
6
42
42
28
Yb(SPh)3(hmpa)3 (13)
this work
(η-C5Me5)2Yb(SPh)(NH3) (15)
[{Yb(hmpa)3}2(µ-SPh)3][SPh] (8)
Yb(SC6H2But3-2,4,6)2(dme)2 (18)
[Yb(µ-SPh)(η5-C4Me4P)(thf)2]2 (5)
Yb(SPh)2(py)4 (4)
41
this work
6
29
2
101.6(3)
a Ar ) 2,4,6-triisopropylphenyl. b Averaged value in the complex. c Bonding mode of the thiolete ligand. d CN ) coordination number.
η-Cyclopentadienyl and η-cyclooctatetraenyl may be taken as occupying three and four coordination sites around the metal, respectively.
Table 4. Crystal Data and Data Collection Parameters
complex
formula
crystal system
space group
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
8
11
13
C60H128O6N18P6S4Yb2
orthorhombic
P212121
21.057(9)
25.963(7)
16.442(8)
C40H77O4N9P3S3Sm
triclinic
P1h
C40H77O4N9P3S3Yb
triclinic
P1h
14.719(3)
17.989(2)
11.344(2)
97.91(1)
110.30(2)
78.40(1)
2751.9(9)
2
14.565(2)
17.961(2)
11.302(1)
97.72(1)
110.49(1)
78.37(1)
2706.0(7)
2
8988(5)
4
Z
D
calcd, g/cm
1.373
23.19
5848
865
0.040
0.039
1.312
13.14
7111
536
0.045
0.041
1.363
19.76
9837
536
0.031
0.035
abs coeff, cm-1
unique data [I > 3σ(I)]
no. of variables
Ra
b
Rw
2
a R ) ∑||Fo| - |Fc||/∑|Fo|. b Rw ) [∑w(|Fo| - |Fc|)2/∑wFo ]1/2
.
Synthesis of [Eu(SAr)(µ-SAr)(thf)3]2 (2). This complex was
prepared and isolated in a manner similar to that of 1. The total yield
was 56%. Mp >300 °C (dec). Anal. Calcd for C38H62O2S2Eu: C,
59.51; H, 8.15. Found: C, 59.10; H, 8.51.
(13% yield), mp 162-164 °C (dec). Anal. Calcd for C30H64-
EuN9O3P3S2: C, 39.69; H, 7.11; N, 13.88. Found: C, 37.16; H, 7.07;
N, 13.38.
Synthesis of [{Yb(hmpa)3}2(µ-SPh)3][SPh] (8). This complex was
prepared and isolated in a manner similar to that of 6, as dark red
crystals (46% yield), mp 135-137 °C (dec). Anal. Calcd for
C30H64N9O3P3S2Yb: C, 38.79; H, 6.94; N, 13.57. Found: C, 38.65;
H, 7.01; N, 13.33. 1H NMR (270 MHz, THF-d8, 30 °C) δ 7.48 (d, 4
H, o-H), 6.74 (m, 4 H, m-H), 6.55 (t, 2 H, p-H), 2.95 (d, 54 H, Me-
(hmpa)).
Synthesis of Yb(SAr)2(py)4 (3). To a suspension of ytterbium metal
(172 mg, 0.99 mmol) with a solution of bis(2,4,6-triisopropylphenyl)
disulfide (435 mg, 0.92 mmol) in THF (40 mL) was added a catalytic
amount of iodine (5 mg, 0.02 mmol). The reaction mixture was stirred
at 50 °C for 24 h. After removal of an excess of ytterbium metal, the
addition of pyridine (1 mL) to the solution caused an immediate change
of the color from orange yellow to black. Recrystallization afforded
black microcrystals of 3 (407 mg, 46% yield), mp 170-215 °C (dec).
Anal. Calcd for C50H66N4S2Yb: C, 62.54; H, 6.93; N, 5.83. Found:
C, 61.85; H, 6.85; N, 6.25. 1H NMR (270 MHz, THF-d8, 30 °C) δ
8.56 (s, 8 H, py), 7.67 (t, 4 H, py), 7.26 (m, 8 H, py), 6.73 (s, 4 H,
m-H), 4.23 (brs, 4 H, o-CHMe2), 2.75 (brs, 2 H, p-CHMe2), 1.18 (m,
36 H, o- and p-CHMe2).
Synthesis of Sm(SAr)3(py)3 (9a). From Sm Metal. To samarium
metal powder (151 mg, 1.00 mmol) and bis(2,4,6-triisopropylphenyl)
disulfide (727 mg, 1.54 mmol) in THF (40 mL) was added a catalytic
amount of iodine (6 mg, 0.02 mmol). Stirring the mixture at 50 °C
for 24 h afforded a red-orange solution. After removal of a small
amount of insoluble impurities, pyridine (1 mL) was added. Concen-
tration, addition of hexane, and cooling to -20 °C afforded orange
microcrystals of 9a (305 mg, 28% yield). Further concentration and
cooling the mother liquor gave a second crop. The total yield was
39%. Mp 160-164 °C. Anal. Calcd for C60H84N3S3Sm: C, 65.88;
H, 7.74; N, 3.84. Found: C, 65.12; H, 7.62; N, 3.76. 1H NMR (270
MHz, THF-d8, 30 °C) δ 8.45 (d, 6 H, py), 7.64 (t, 3 H, py), 7.22 (m,
6 H, py), 6.70 (s, 6 H, m-H), 4.76 (m, 6 H, o-CHMe2), 2.67 (m, 3 H,
p-CHMe2), 1.28 (d, 36 H, o-CHMe2), 1.15 (d, 18 H, p-CHMe2).
Synthesis of [{Sm(hmpa)3}2(µ-SPh)3][SPh] (6). To samarium
metal (912 mg, 6.07 mmol) and diphenyl disulfide (684 mg, 3.13 mmol)
in THF (30 mL) was added a catalytic amount of iodine (20 mg, 0.08
mmol). The reaction mixture was stirred at 50 °C for 24 h to give a
mixture of a black powder and unreacted metal. When the HMPA
(2.20 mL, 12.6 mmol) was added to the reaction mixture, the black
powder gradually dissolved within 1 h. Removal of the metal followed
by recrystallization gave black prisms of 5 (241 mg, 8% yield). Further
concentration and cooling the mother liquor gave a second crop. The
total yield was 29%. Mp 87-93 °C (dec). Anal. Calcd for
C30H64N9O3P3S2Sm: C, 39.76; H, 7.12; N, 13.91. Found: C, 37.65;
H, 7.20; N, 13.45.
From complex 1. To a dark green solution of 1 (258 mg, 0.15
mmol) in THF (3 mL) was added a solution of bis(2,4,6-triisopropy-
lphenyl) disulfide (75 mg, 0.16 mmol) in THF (1 mL). Stirring the
mixture at room temperature for 12 h afforded a orange solution.
Addition of pyridine (0.1 mL) followed by concentration, addition of
hexane, and cooling to -20 °C afforded orange crystals of 9a (114
mg, 34% yield).
Synthesis of [{Eu(hmpa)3}2(µ-SPh)3][SPh] (7). This complex was
prepared and isolated in a manner similar to that of 6, as yellow crystals

98 Inorganic Chemistry, Vol. 35, No. 1, 1996
Table 5. Atomic Coordinates of Complex 8
Mashima et al.
atom
x
y
z
Beq
atom
x
y
z
Beq
Yb(1)
Yb(2)
S(1)
S(2)
S(3)
S(4)
P(1)
P(2)
P(3)
0.01299(2)
0.03126(2)
0.1056(2)
-0.0679(2)
0.0241(2)
0.4429(4)
0.0253(2)
-0.1419(2)
0.1225(2)
0.1569(2)
-0.0937(2)
0.0499(2)
0.0250(5)
-0.0796(4)
0.0749(4)
0.1065(5)
-0.0449(4)
0.0512(5)
0.0839(9)
0.031(1)
-0.0387(8)
-0.1475(7)
-0.2050(6)
-0.1508(7)
0.1326(6)
0.1928(6)
0.1046(8)
0.1448(7)
0.2254(6)
0.1607(7)
-0.1595(7)
-0.0713(7)
-0.1069(8)
-0.0188(7)
0.1016(7)
0.0663(8)
0.1842(7)
0.2340(8)
0.2987(8)
0.3118(9)
0.2632(8)
0.2021(7)
-0.0914(9)
-0.0463(9)
-0.070(2)
-0.130(2)
-0.174(1)
-0.152(1)
0.17582(2)
0.17608(2)
0.2198(1)
0.2131(1)
0.0935(1)
0.0487(3)
0.2942(2)
0.1348(2)
0.0954(2)
0.0928(2)
0.1294(2)
0.2980(2)
0.2464(3)
0.1512(4)
0.1273(4)
0.1280(4)
0.1512(3)
0.2487(4)
0.3295(7)
0.2846(6)
0.3258(9)
0.1514(7)
0.1585(5)
0.0724(5)
0.0363(5)
0.1205(5)
0.0874(7)
0.0800(6)
0.1167(6)
0.0349(5)
0.1603(7)
0.1338(5)
0.0689(6)
0.3087(5)
0.2966(5)
0.3467(5)
0.2003(6)
0.2352(6)
0.2179(9)
0.1667(10)
0.1332(8)
0.1482(6)
0.2779(6)
0.3182(7)
0.3676(8)
0.3819(9)
0.343(1)
0.85014(3)
0.60822(3)
0.7394(2)
0.7188(2)
0.7286(2)
0.7616(7)
0.9857(3)
0.9481(3)
0.9813(3)
0.5086(3)
0.4604(3)
0.4846(3)
0.9383(5)
0.9190(6)
0.9404(6)
0.5386(6)
0.5141(5)
0.5301(5)
0.962(1)
3.94(1)
3.94(1)
4.77(9)
4.77(9)
4.70(8)
18.4(4)
5.4(1)
5.7(1)
5.1(1)
5.2(1)
6.0(1)
5.2(1)
5.3(2)
5.9(3)
5.9(3)
5.9(3)
5.5(3)
6.2(3)
11.8(6)
10.8(6)
14.4(8)
8.5(5)
6.6(4)
7.8(4)
6.4(4)
6.4(4)
8.9(5)
7.7(4)
6.9(4)
6.9(4)
8.5(5)
6.8(4)
8.5(5)
8.3(5)
7.8(4)
8.6(5)
4.9(4)
6.7(5)
8.4(6)
9.1(7)
8.2(6)
6.0(5)
6.1(5)
9.3(6)
13(1)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(37)
C(38)
C(39)
C(40)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
C(47)
C(48)
C(49)
C(50)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
C(57)
C(58)
C(59)
C(60)
-0.0423(9)
-0.1022(10)
-0.1538(9)
-0.142(1)
-0.084(1)
-0.0315(9)
0.524(1)
0.546(2)
0.609(3)
0.651(2)
0.626(2)
0.0514(5)
0.0675(7)
0.0335(10)
-0.018(1)
-0.0356(8)
-0.0021(6)
0.0421(6)
0.022(1)
0.013(2)
0.029(1)
0.050(1)
0.0564(8)
0.3290(8)
0.357(2)
0.248(1)
0.313(1)
0.7190(8)
0.703(1)
0.697(2)
0.707(2)
0.723(2)
0.727(1)
0.744(2)
0.671(2)
0.662(3)
0.719(3)
0.786(2)
0.800(1)
0.887(1)
1.038(3)
1.116(1)
1.133(2)
0.948(2)
0.970(2)
1.091(1)
1.087(1)
0.925(2)
0.820(1)
0.941(1)
0.932(1)
0.862(1)
0.967(2)
0.982(1)
0.966(1)
1.134(1)
1.112(1)
0.369(1)
0.365(1)
0.533(1)
0.517(1)
0.530(2)
0.634(1)
0.401(2)
0.545(1)
0.3347(10)
0.304(1)
0.500(1)
0.473(1)
0.494(1)
0.370(2)
0.373(1)
0.373(1)
0.598(2)
0.537(2)
5.4(4)
7.6(6)
10.9(8)
11.0(9)
11.2(8)
7.4(5)
8.9(7)
11.7(10)
16(1)
15(1)
13(1)
11.3(8)
9.5(6)
38(2)
P(4)
P(5)
P(6)
0.563(2)
0.1144(9)
0.117(1)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
N(9)
N(10)
N(11)
N(12)
N(13)
N(14)
N(15)
N(16)
N(17)
N(18)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
0.068(1)
14(1)
26(1)
12.2(9)
34(2)
-0.026(2)
-0.094(1)
-0.027(2)
-0.200(1)
-0.1032(9)
-0.2242(10)
-0.2169(8)
-0.2070(10)
-0.0931(10)
0.1548(9)
0.0827(10)
0.2523(8)
0.1998(8)
0.146(1)
0.310(1)
0.388(1)
0.133(1)
14.0(9)
11.1(7)
13.8(9)
8.9(6)
11.5(8)
8.6(6)
7.5(5)
10.7(7)
9.2(6)
8.8(6)
16(1)
12.9(9)
9.5(7)
11.9(8)
8.0(5)
10.2(7)
12.1(8)
10.2(7)
17(1)
12.0(8)
9.0(6)
11.2(7)
9.2(7)
12.7(9)
12.9(10)
16(1)
11.3(8)
13.6(9)
13.2(9)
19(1)
1.0809(10)
0.977(1)
0.1817(10)
0.2102(9)
0.1454(8)
0.0447(9)
0.0403(7)
0.0294(6)
-0.0017(8)
0.0939(8)
0.1764(8)
0.061(1)
0.1043(9)
0.0981(8)
0.0486(10)
0.1714(8)
0.0903(8)
-0.0025(8)
0.0304(8)
0.173(1)
1.0439(9)
0.9026(10)
0.9334(10)
0.9418(10)
0.9710(8)
1.0752(9)
0.4136(9)
0.5252(9)
0.5534(9)
0.469(1)
0.050(1)
0.094(1)
0.186(1)
0.3660(7)
0.483(1)
0.2340(7)
0.2853(8)
0.1123(10)
0.182(1)
-0.2017(9)
-0.1861(8)
-0.0442(9)
-0.084(1)
-0.051(1)
-0.165(1)
-0.0767(8)
-0.031(1)
0.120(1)
0.4462(9)
0.4136(9)
0.5437(10)
0.7491(8)
0.7535(9)
0.759(1)
0.764(1)
0.759(1)
0.749(1)
0.722(1)
0.733(1)
0.736(2)
0.734(2)
0.715(2)
0.173(1)
0.1814(7)
0.0949(8)
0.0368(8)
0.0429(9)
0.298(1)
0.331(1)
0.2506(9)
0.342(1)
18(1)
14(1)
8.9(6)
0.127(1)
0.118(1)
0.033(2)
0.3450(8)
0.3951(9)
0.2917(7)
0.713(1)
Synthesis of Sm(SAr)3(py)2(thf) (9b). Complex 9a (348 mg) was
redissolved in THF followed by addition of hexane, concentration, and
cooling the mixture to -20 °C to give orange crystals (5 mg) of 9b.
Further concentration and cooling of the mother liquor to -20 °C to
gave a second crop (83 mg). The total yield was 24%. Mp 163-167
°C. Anal. Calcd for C59H87N2OS3Sm: C, 65.20; H, 8.07; N, 2.58.
Found: C, 63.86; H, 8.09; N, 2.54. 1H NMR (270 MHz, THF-d8, 30
°C) δ 8.45 (d, 4 H, py), 7.64 (t, 2 H, py), 7.21 (m, 4 H, py), 6.71 (s,
6 H, m-H), 4.77 (m, 6 H, o-CHMe2), 2.68 (m, 3 H, p-CHMe2), 1.29
(d, 36 H, o-CHMe2), 1.15 (d, 18 H, p-CHMe2).
H, 7.28; N, 11.69. 1H NMR (270 MHz, THF-d8, 30 °C) δ 7.01 (m, 3
H, p-H), 6.76 (d, 6 H, o-H), 6.35 (brs, 6 H, m-H), 2.58 (d, 54 H, Me-
(hmpa)).
Synthesis of Eu(SPh)3(hmpa)3 (12). This complex was prepared
and isolated in a manner similar to that of 11, as dark red crystals
(70% yield), mp 128-131 °C. Anal. Calcd for C40H77EuN9O4P3S3:
C, 44.11; H, 7.13; Eu, 13.95; N, 11.57. Found: C, 43.96; H, 7.14; N,
11.81. 1H NMR (270 MHz, THF-d8, 30 °C) δ 11.63 (brs, 6 H, m- or
o-H), 8.81 (brs, 3 H, p-H), 6.66 (brs, 6 H, m- or o-H), 1.90 (d, 54 H,
Me(hmpa)).
Synthesis of Yb(SPh)3(hmpa)3 (13). This complex was prepared
and isolated in a manner similar to that of 11, as yellow crystals (79%
yield), mp 187-190 °C. Anal. Calcd for C40H77N9O4P3S3Yb: C,
43.27; H, 6.99; N, 11.35. Found: C, 43.27; H, 7.11; N, 11.39.
Synthesis of Yb(SAr)3(py)3 (10). This complex was prepared and
isolated in a manner similar to that of 9a, as red crystals. The total
yield was 30%. Mp 198-201 °C. Anal. Calcd for C60H84N3S3Yb:
C, 64.54; H, 7.58; N, 3.76. Found: C, 63.70; H, 7.77; N, 3.34.
Crystallographic Data Collections and Structure Determination
of 8, 11, and 13. The crystals of 8, 11, and 13 suitable for X-ray
diffraction sealed in glass capillaries under argon atmosphere were
mounted on a Rigaku AFC-5R four-circle diffractometer for data
collection using Mo KR radiation. Three standard reflections were
chosen and monitored every 150 reflections. Measured nonequivalent
reflections with I > 3.0σ(I) were used for the structure determination.
Empirical absorption correction was carried out based on an azimuthal
scan.
Synthesis of Sm(SPh)3(hmpa)3 (11). To samarium metal (402 mg,
2.67 mmol), diphenyl disulfide (883 mg, 4.05 mmol), and HMPA (1.40
mL, 8.05 mmol) in THF (30 mL) was added a catalytic amount of
iodine (21 mg, 0.08 mmol). The reaction mixture was stirred at 50 °C
for 24 h to give a brown solution. Removal of a small amount of
insoluble impurities followed by cooling to -20 °C afforded colorless
crystals of 11 (2.10 g, 77% yield), mp 142-146 °C. Anal. Calcd for
C40H77N9O4P3S3Sm: C, 44.17; H, 7.14; N, 11.59. Found: C, 43.96;

Arenethiolate Complexes of Lanthanides
Inorganic Chemistry, Vol. 35, No. 1, 1996 99
Table 6. Atomic Coordinates of Complex 11
atom
x
y
z
Beq
atom
x
y
z
Beq
Sm(1)
S(1)
S(2)
S(3)
P(1)
P(2)
P(3)
O(1)
O(2)
O(3)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
N(9)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
0.25566(3)
0.2191(2)
0.2848(2)
0.2886(2)
-0.0136(1)
0.1996(2)
0.5170(1)
0.0894(3)
0.2209(3)
0.4167(3)
-0.0194(5)
-0.0749(5)
-0.0684(5)
0.1315(5)
0.2986(5)
0.1376(5)
0.5090(5)
0.5701(4)
0.5855(4)
0.2990(6)
0.3130(6)
0.3740(8)
0.4225(8)
0.4122(9)
0.3499(8)
0.2136(5)
0.1951(6)
0.1416(7)
0.23309(2)
0.3835(1)
0.0720(1)
0.2611(1)
0.2883(1)
0.1620(1)
0.2272(1)
0.2510(2)
0.2040(2)
0.2214(2)
0.3670(4)
0.3035(4)
0.2328(4)
0.0979(3)
0.1189(4)
0.2226(3)
0.2850(4)
0.1429(3)
0.2590(4)
0.4433(4)
0.4557(5)
0.5039(6)
0.5411(6)
0.5299(6)
0.4801(5)
0.0325(4)
0.0616(4)
0.0247(6)
0.03776(4)
0.1393(3)
0.0019(2)
-0.1806(2)
-0.1361(2)
0.2991(2)
0.2501(2)
-0.0724(4)
0.2088(4)
0.1578(4)
-0.1932(7)
-0.0374(8)
-0.2573(7)
0.2246(6)
0.3994(6)
0.3756(6)
0.3713(6)
0.2988(6)
0.1904(6)
0.1367(8)
0.0272(9)
0.026(1)
3.251(8)
6.95(7)
4.89(5)
4.94(5)
4.83(5)
4.37(5)
4.25(5)
4.4(1)
4.3(1)
4.2(1)
6.7(2)
7.2(2)
6.7(2)
4.8(2)
5.3(2)
5.2(2)
5.1(2)
5.1(2)
5.0(2)
4.7(2)
6.1(3)
8.3(4)
8.9(4)
9.2(4)
7.4(3)
3.9(2)
5.4(2)
7.0(3)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
0.1066(7)
0.1252(6)
0.1773(6)
0.4102(5)
0.4562(6)
0.4621(6)
0.5553(7)
0.5495(7)
0.5992(6)
0.0451(8)
-0.072(1)
-0.0333(7)
-0.1786(8)
-0.1387(9)
-0.0568(8)
0.1624(7)
0.0739(7)
0.3264(7)
0.3709(7)
0.1506(7)
0.0582(6)
0.6805(7)
0.4321(7)
0.5777(7)
0.6430(7)
0.5631(6)
0.5467(6)
-0.0406(6)
-0.0684(5)
-0.0333(4)
0.2232(4)
0.1506(4)
0.2632(4)
0.2329(6)
0.1218(5)
0.1618(6)
0.3735(7)
0.4372(6)
0.3330(6)
0.3012(9)
0.2583(7)
0.1536(5)
0.2984(5)
0.2016(5)
0.1270(5)
0.0695(5)
0.0202(5)
0.1118(5)
0.2237(5)
0.2858(5)
0.3352(5)
0.1307(5)
0.0755(5)
0.3274(5)
-0.3644(9)
-0.2524(10)
-0.1420(8)
-0.1766(6)
-0.1369(7)
-0.2197(7)
-0.2221(9)
-0.1396(8)
-0.1821(9)
-0.258(1)
-0.170(2)
0.089(1)
-0.076(1)
-0.376(1)
-0.2437(10)
0.4175(9)
0.4340(9)
0.5350(8)
0.3514(8)
0.2564(9)
0.1034(8)
0.187(1)
7.0(3)
6.2(3)
4.9(2)
4.1(2)
5.0(2)
5.4(2)
6.8(3)
6.2(3)
7.1(3)
13.7(5)
22.3(8)
9.1(4)
16.7(6)
14.3(5)
10.0(3)
7.8(3)
7.6(3)
7.4(3)
7.9(3)
7.9(3)
6.7(3)
9.8(4)
7.3(3)
8.2(3)
8.7(3)
7.1(3)
7.3(3)
0.135(1)
0.246(1)
0.2476(10)
-0.1401(7)
-0.2548(8)
-0.3665(8)
0.4231(8)
0.4379(8)
0.4222(9)
0.2104(9)
0.1218(9)
Table 7. Atomic Coordinates of Complex 13
atom
x
y
z
Beq
atom
x
y
z
Beq
Yb(1)
S(1)
S(2)
S(3)
P(1)
P(2)
P(3)
O(1)
O(2)
O(3)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
N(9)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
0.25488(1)
0.2182(1)
0.28294(8)
0.28911(8)
-0.00970(8)
0.19817(9)
0.51323(8)
0.0943(2)
0.2200(2)
0.4118(2)
-0.0158(3)
-0.0731(3)
-0.0634(3)
0.1307(3)
0.2984(3)
0.1346(3)
0.5066(3)
0.5682(3)
0.5812(2)
0.2980(3)
0.3118(4)
0.3726(5)
0.4212(5)
0.4102(5)
0.3490(4)
0.2133(3)
0.1944(3)
0.1433(4)
0.232904(9)
0.37976(6)
0.07713(6)
0.26152(6)
0.28745(6)
0.16421(6)
0.22664(6)
0.2500(1)
0.2061(1)
0.2210(1)
0.3670(2)
0.3019(3)
0.2320(2)
0.0991(2)
0.1226(2)
0.2257(2)
0.2851(2)
0.1426(2)
0.2588(2)
0.4410(2)
0.4543(3)
0.5053(3)
0.5430(3)
0.5307(4)
0.4794(3)
0.0367(2)
0.0660(3)
0.0290(3)
0.04246(2)
0.1359(1)
0.00651(9)
-0.1673(1)
-0.1335(1)
0.29791(10)
0.24896(10)
-0.0682(2)
0.2077(2)
0.1575(2)
-0.1899(4)
-0.0370(4)
-0.2558(4)
0.2253(3)
0.4006(3)
0.3729(3)
0.3700(3)
0.2997(3)
0.1874(3)
0.1353(4)
0.0263(5)
0.0277(6)
0.1372(8)
0.2452(7)
0.2461(5)
-0.1390(4)
-0.2538(4)
-0.3654(5)
2.718(3)
5.69(3)
3.96(2)
4.16(2)
4.09(2)
3.63(2)
3.56(2)
3.67(6)
3.75(6)
3.72(6)
5.8(1)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
0.1093(4)
0.1266(4)
0.1781(3)
0.4100(3)
0.4605(4)
0.5530(4)
0.5977(4)
0.5493(4)
0.4565(3)
0.0491(5)
-0.0668(9)
-0.0320(5)
-0.1802(5)
-0.1341(6)
-0.0527(5)
0.1592(4)
0.0694(4)
0.3238(4)
0.3740(4)
0.1505(4)
0.0550(4)
0.6768(4)
0.4294(4)
0.5783(4)
0.6427(4)
0.5617(4)
0.5408(4)
-0.0369(3)
-0.0666(3)
-0.0302(2)
0.2214(2)
0.2625(3)
0.2320(3)
0.1606(4)
0.1187(3)
0.1492(2)
0.3734(4)
0.4380(4)
0.3314(4)
0.2999(6)
0.2585(4)
0.1518(3)
0.3012(3)
0.2035(3)
0.1299(3)
0.0720(3)
0.0217(3)
0.1120(3)
0.2220(3)
0.2862(3)
0.3346(3)
0.1317(3)
0.0754(3)
0.3282(3)
-0.3656(5)
-0.2539(6)
-0.1414(4)
-0.1688(3)
-0.2157(4)
-0.2235(5)
-0.1851(5)
-0.1390(5)
-0.1304(4)
-0.2553(9)
-0.1595(9)
0.0919(6)
-0.0790(9)
-0.3740(7)
-0.2433(6)
0.4148(5)
0.4307(5)
0.5367(4)
0.3569(5)
0.2594(5)
0.1016(5)
0.1823(7)
0.4241(4)
0.4374(5)
0.4248(5)
0.2113(5)
6.1(1)
5.6(1)
4.4(1)
3.54(9)
4.6(1)
6.0(1)
6.1(1)
5.7(1)
4.2(1)
11.9(3)
17.0(4)
7.7(2)
14.6(3)
10.8(2)
7.9(2)
6.6(2)
6.6(2)
6.6(2)
6.7(2)
6.7(2)
5.5(1)
8.1(2)
6.0(1)
6.8(2)
7.4(2)
5.8(1)
6.0(1)
6.2(1)
5.53(10)
4.24(9)
4.61(9)
4.62(9)
4.57(9)
4.46(8)
4.41(9)
4.2(1)
5.3(1)
7.0(2)
7.9(2)
7.8(2)
6.2(1)
3.25(8)
4.6(1)
0.1202(5)
6.2(1)
The structure of 8 was solved by direct methods46 and those of 11
and 13 were solved by the heavy-atom Patterson methods.46,47 In the
final refinement cycle (full-matrix), hydrogen atom coordinates were
included at idealized positions, and the hydrogen atoms were given
the same temperature factor as that of the carbon atom to which they
were bonded. All calculations were performed by using the TEXSAN
crystallographic software package. The THF molecule in 11 and 13
showed disordered form, and the occupancy of the disordered atoms
was fixed at 0.5. All other non-hydrogen atoms were refined
anisotropically. All hydrogen atoms were not refined.
The pertinent details of data collection and the final cell dimensions
for 8, 11, and 13 are given in Table 4. Atomic coordinates of 8, 11,
and 13 are listed in Tables 5, 6 and 7, respectively.
Acknowledgment. A.N. thanks to the Ministry of Education,
Science and Culture, Japan, for support of this research
(Specially Promoted Research No. 06101004).
Supporting Information Available: Tables of complete crystal
data, hydrogen atom coordinates and isotropic thermal parameters,
anisotropic thermal parameters for non-hydrogen atoms, and bond
distances and angles and ORTEP drawings for 8, 11, and 13 (37 pages).
Ordering information is given on any current masthead page.
(46) Fan, H.-F. SAPI91: Structure Analysis Programs with Intelligent
Control. Rigaku Corporation, Tokyo, Japan, 1991.
(47) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.; Garcia-
Granda, S.; Gould, R. O.; Smits, J. M. M.; Smykalla, C. PATTY:
The DIRDIF program system, Tecnical Report of the Crystallography
Laboratory. University of Nijmegen, The Netherlands, 1992.
IC950050I