Transition metal complexes with sulfur ligands, 134 [(+)] - Synthesis of the tetradentate thioether amine and thioether thiolate ligands 1,2 bis(2 aminophenylthio)phenylene and 1,2 bis(2 mercaptophenylthio)phenylene and some representative six-coordinate ruthenium and osmium complexes

Article abstract of DOI:10.1002/(sici)1099-0682(19990202)1999:2<333::aid-ejic333>3.0.co;2-r

In search of a tetradentate thioether thiolate ligand that is more stable toward reductive C-S bond cleavage than the parent ligand 'S₄'-H₂ ['S₄'-H₂ = 1,2-bis(2-mercaptophenylthio)ethane], the novel tris-phenylene ligand 'tpS₄'H₂ (3) ['tpS₄'-H₂ = 1,2-bis(2-mercaptophenylthio)phenylene] was synthesized via the nitro and amine compounds 'tpS₂(NO₂)₂' (1) and 'tpS₂(NH₂)₂' (2). The coordination of 'tpS₄'^2- to ruthenium centers resulted in the formation of six-coordinate [Ru(L)(PR₃)('tpS₄')] complexes (R = Et, L = PEt₃ 4; R = Ph, L = PPh₃ 5, CO 6, DMSO 7). The X-ray structure analyses of 4 and 6 revealed that the thiolate donors occupy trans positions; consequently the 'tpS₄'^2- ligand coordinates in the same way as the 'S₄'^2- ligand. The stability of the 'tpS₄'^2- ligand toward reductive C- S cleavage reactions was shown by the synthesis of [Os(PEt₃)₂('tpS₄')] (8). In contrast to [Os(PEt₃)₂('S₄')], 8 is stable for unlimited periods of time. The X-ray structure analysis of [Ru(Cl)₂(PPh₃)('tpS₂(NH₂)₂')] (9) demonstrates that the potentially tetradentate ligand 'tpS₂(NH₂)₂' coordinates in 9 through three donors leaving one NH₂ donor dangling.

Full text of DOI:10.1002/(sici)1099-0682(19990202)1999:2<333::aid-ejic333>3.0.co;2-r

FULL PAPER
Transition Metal Complexes with Sulfur Ligands, 134[°]
Synthesis of the Tetradentate Thioether Amine and Thioether Thiolate
Ligands ЈtpS2(NH2)2Ј and ЈtpS4Ј-H2 and Some Representative
Six-Coordinate Ruthenium and Osmium Complexes [ЈtpS2(NH2)2Ј ؍
1,2-Bis(2-aminophenylthio)phenylene; ЈtpS4Ј2– ؍
1,2-Bis(2-mercaptophenylthio)phenylene(2–)]
Dieter Sellmann,*[a] Klaus Engl,[a] Torsten Gottschalk-Gaudig,[a] and Frank W. Heinemann[a]
Dedicated to Professor Bernt Krebs on the occassion of his 60th birthday
Keywords: Cleavage reactions / C–S cleavage / Ligand synthesis / Osmium / Ruthenium / S ligands
In search of a tetradentate thioether thiolate ligand that is
more stable toward reductive C–S bond cleavage than the
analyses of 4 and 6 revealed that the thiolate donors occupy
trans positions; consequently the ЈtpS4Ј2– ligand coordinates
in the same way as the ЈS4Ј2– ligand. The stability of the
ЈtpS4Ј2– ligand toward reductive C–S cleavage reactions was
shown by the synthesis of [Os(PEt3)2(ЈtpS4Ј)] (8). In contrast
to [Os(PEt3)2(ЈS4Ј)], 8 is stable for unlimited periods of time.
The X-ray structure analysis of [Ru(Cl)2(PPh3)(ЈtpS2(NH2)2Ј)]
(9) demonstrates that the potentially tetradentate ligand
ЈtpS2(NH2)2Ј coordinates in 9 through three donors leaving
one NH2 donor dangling.
parent ligand ЈS4Ј-H2 [ЈS4Ј-H2
=
1,2-bis(2-mercapto-
phenylthio)ethane], the novel tris-phenylene ligand ЈtpS4Ј-
H2 (3) [ЈtpS4Ј-H2 = 1,2-bis(2-mercaptophenylthio)phenylene]
was synthesized via the nitro and amine compounds
ЈtpS2(NO2)2Ј (1) and ЈtpS2(NH2)2Ј (2). The coordination of
ЈtpS4Ј2– to ruthenium centers resulted in the formation of six-
coordinate [Ru(L)(PR3)(ЈtpS4Ј)] complexes (R = Et, L = PEt3 4;
R = Ph, L = PPh3 5, CO 6, DMSO 7). The X-ray structure
The tetradentate thioether thiolate ligand ‘S4’ϪH2 small species is strongly influenced by the [M(ЈS4Ј)] cores.
[ϭ 1,2-bis(2-mercaptophenylthio)ethane] exhibits a rich co- In some of these reactions, the ЈS4Ј2Ϫ ligand appears to be-
ordination chemistry. It binds to numerous transition met- have as a ЈspectatorЈ ligand only, yielding a robust [M(ЈS4Ј)]
als, e.g. Fe, Ru, Os, Cr, Mo, W, Ni, and the resulting core, although in all reactions involving protons, the
[M(ЈS4Ј)] complex fragments are able to coordinate a large Brønsted basicity of the thiolate donors has been shown to
variety of coligands to give six-coordinate complexes of the be pivotal.[1b,1g,2,3] In other reactions, the ЈS4Ј2Ϫ ligand can
type [M(L)(LЈ)(ЈS4Ј)].[1]
experience severe changes. Coordination of the ЈS4Ј2Ϫ li-
gand to very electron-rich metal centers and UV irradiation
or treatment of [M(ЈS4Ј)] complexes with strongly reducing
reagents frequently causes the reductive elimination of the
C2H4 bridge as ethylene. For example, the reaction of ЈS4Ј2Ϫ
with [MoCl2(PMe3)4] gives the MoIV complex [Mo(P-
Me3)2(S2C6H4)2] and C2H4,[4] [Os(PEt3)2(ЈS4Ј)] readily re-
leases C2H4 to give [Os(PEt3)2(S2C6H4)2],[1e] UV irradiation
of [Ru(CO)(PCy3)(ЈS4Ј)] yields [Ru(PCy3)(S2C6H4)2] and
C2H4,[5] and the reduction of [Fe(CO)2(ЈS4Ј)] by metallic
sodium gives the FeII complex [Fe(S2C6H4)2]2Ϫ and C2H4.[6]
The partial cleavage of SϪC bonds is observed when
[Ru(PPh3)2(ЈS4Ј)] is treated with NO.[7] In this case, [Ru-
(NO)(PPh3)(S2C6H4)(CH2ϭCHϪSC6H4S)] forms, which
contains a vinyl thioether thiolate ligand. All these reac-
tions represent the reversal of the ЈS4Ј2Ϫ formation, which
The coligands L or LЈ range from hard ligands such as
halides or oxide to soft ligands such as CO or phosphanes.
The coligands also include a large number of biologically
relevant small species, for example, N2H2, N2H3, N2H4,
NH3, NOϩ, NO, NH2O, H2, HϪ, CH3Ϫ, CH3COϪ, H2S, or
S2. The activation or stabilization and the reactivity of these
2Ϫ
is synthesized via template alkylation of S2C6H4 by 1,2-
[°]
Part 133: D. Sellmann, S. Emig, F. W. Heinemann, F. Knoch,
C2H4Br2.[1a] The ЈS4Ј2Ϫ cleavage reactions are usually un-
wanted. They can be traced back to the π acidity of the
thioether donor functions and the partial occupation of
antibonding CϪS(thioether) σ* orbitals by metal d-elec-
trons.[8] We have now tried to synthesize a ligand which
Z. Naturforsch., in press.
[a]
Institut für Anorganische Chemie der Universität Erlangen-
Nürnberg
Egerlandstraße 1, D-91058 Erlangen, Germany
Fax: (internat.) ϩ 49(0)9131/8527367
E-mail: sellmann@anorganik.chemie.uni-erlangen.de
Eur. J. Inorg. Chem. 1999, 333Ϫ339
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
1434Ϫ1948/99/0202Ϫ0333 $ 17.50ϩ.50/0
333

D. Sellmann, K. Engl, T. Gottschalk-Gaudig, F. W. Heinemann
FULL PAPER
maintains the donor functions and coordination pattern of H2 (3). The compounds 1, 2, and 3 were characterized by
the ЈS4Ј2Ϫ ligand, but is stable toward strong reducing re- elemental analysis and spectroscopic methods. The molecu-
agents and photolysis. For this purpose, the C2H4 bridge in lar structures of 1 and 2 were determined by X-ray diffrac-
ЈS4Ј2Ϫ has been replaced by an o-phenylene bridge. In order tion.
to clearly distinguish the target from the parent ligand and
Scheme 2 summarizes the syntheses of ruthenium and
for indicating the presence of the phenylene entities, we use osmium complexes which were obtained with ЈtpS4Ј2Ϫ. In
the acronym ЈtpS4Ј-H2.
one experiment also the coordination of ЈtpS2(NH2)2Ј (2)
was investigated.
In orienting experiments, the coordination of ЈtpS4Ј2Ϫ to
electron-rich RuII and OsII complexes was tested.
Results
The target ligand ЈtpS4Ј-H2 (3) was synthesized by the
route given in Scheme 1.
Scheme 2. Synthesis of ЈtpS4Ј2Ϫ ruthenium and osmium complexes
and of [Ru(Cl)2(PPh3)(ЈtpS2(NH2)2Ј)]; (a) [Ru(Cl)2(DMSO)4]/PEt3/
MeOH/1 h reflux; (b) [RuCl2(PPh3)3]/THF/4 h at room tempera-
ture/5 min reflux; (c) CH2Cl2/CO/12 h/room temperature; (d)
DMSO/5 min at 40°C; (e) OsCl3 · x H2O/PEt3/MeOH/2 h reflux;
(f) THF/1 h reflux
The reaction of dianionic ЈtpS4Ј2Ϫ, which was routinely
obtained from ЈtpS4Ј-H2 (3) and NaOMe or BuLi, with
[Ru(Cl)2(DMSO)4] in the presence of excess PEt3 yielded
[Ru(PEt3)2(ЈtpS4Ј)] (4). Heating to reflux was necessary in
order to drive the reaction to completeness. Treatment of
Scheme 1. Synthesis of ЈtpS4Ј-H2; i: MeOH/12 h/reflux; ii: Zn/
NH4Cl/THF/12 h/reflux; iii: 1. NaNO2/H2SO4/H2O/0°C; 2.
KSC(S)OEt/H2O/85°C; 3. KOH/EtOH/12 h/reflux; 4. HCl/H2O, 5.
LiOMe/Niac2 · 4 H2O, 6. HCl
Nucleophilic substitution of fluorine in 1,2-C6H4(F)- [RuCl2(PPh3)3] with ЈtpS4Ј-Li2 in boiling THF gave
(NO2)[9] by the thiolate functions of Na2S2C6H4 yielded the [Ru(PPh3)2(ЈtpS4Ј)] (5). Complex 5 shows that also two
tris-phenylene nitro compound ЈtpS2(NO2)2Ј (1) in practi- sterically demanding phosphanes can bind to the
cally quantitative yield. Reduction of the nitro groups in 1 [Ru(ЈtpS4Ј)] fragment. One PPh3 ligand in 5 is labile and
by Zn/NH4Cl[10] gave the diamine-dithioether ЈtpS2(NH2)2Ј readily exchanges for CO at ambient temperatures to give
(2). Diazotisation of the NH2 groups of 2 and subsequent [Ru(CO)(PPh3)(ЈtpS4Ј)] (6). The PPh3 ligand also exchanges
reaction of the resulting bis-diazonium salt with for DMSO at slightly elevated temperature (40°C) to give
KSC(S)(OEt), hydrolysis and acidification[11] yielded a [Ru(DMSO)(PPh3)(ЈtpS4Ј)] (7). The DMSO ligand in 7 is
1
brown oil containing ЈtpS4Ј-H2 (3) and a mixture of other also labile. H-NMR spectra of 7 in [D6]DMSO show only
compounds. Purification of this brown oil proved difficult. one DMSO signal at δ ϭ 2.57 indicating exchange of coor-
After many unsuccessful attempts applying conventional dinated DMSO and [D6]DMSO solvent molecules, which is
techniques, isolation of pure ЈtpS4Ј-H2 (3) was finally rapid on the NMR time-scale.
achieved by coordination to NiII salts and subsequent hy-
A critical test for the inertness of ЈtpS4Ј2Ϫ toward CϪS
drolysis of the resulting nickel complex. Treatment of the cleavage reactions was its reaction with OsCl3 · x H2O in
brown oil with LiOMe and Niac2 · 4 H2O yielded a red- the presence of excess PEt3. It yielded, although in low
brown microcrystalline solid which was analyzed as yield, [Os(PEt3)2(ЈtpS4Ј)] (8). Subsequent NMR spectro-
[Ni(ЈtpS4Ј)]2 · THF · 0.5 MeOH. Hydrolysis with hydro- scopic investigations showed that 8 is stable in solution for
chloric acid gave a colorless analytically pure oil of ЈtpS4Ј- unlimited periods of time and contrasts [Os(PEt3)2(ЈS4Ј)]
334
Eur. J. Inorg. Chem. 1999, 333Ϫ339

Transition Metal Complexes with Sulfur Ligands, 134
FULL PAPER
which rapidly releases C2H4 to give [Os(PEt3)2(S2- tons of the uncoordinated NH2 group give rise to a singlet,
C6H4)2].[1e]
while the protons of the coordinated NH2 group give rise
The comparison of the reactions b) and f) in Scheme 2 to two doublets, because the NH protons are nonequivalent
shows that ЈtpS2(NH2)2Ј (2) has poorer coordinating capa- in C1-symmetrical 9. In addition, only the uncoordinated
bilities than ЈtpS4Ј2Ϫ (3). Even after prolonged heating to NH2 group shows Hϩ/Dϩ exchange with D2O.
reflux, the THF mixture of RuCl2(PPh3)3 and ЈtpS2(NH2)2Ј
The molecular structures of ЈtpS2(NO2)2Ј (1), ЈtpS2-
yielded exclusively [Ru(Cl)2(PPh3)(ЈtpS2(NH2)2Ј)] (9) in (NH2)2Ј (2) [Ru(Cl)2(PPh3)(ЈtpS2(NH2)2Ј)] (9), [Ru(P-
which the potentially tetradentate ЈtpS2(NH2)2Ј (2) utilizes Et3)2(ЈtpS4Ј)] · 0.5 Et2O (4 · 0.5 Et2O), and [Ru(CO)-
only three of its four donor functions.
(PPh3)(ЈtpS4Ј)] · CH2Cl2 (6 · CH2Cl2) are depicted in Figure
1. Table 1 lists selected distances and angles.
Characterization of the Compounds and Complexes
All compounds were characterized by elemental analysis
and spectroscopic methods, the molecular structures of
ЈtpS2(NO2)2Ј (1), ЈtpS2(NH2)2Ј (2), [Ru(PEt3)2(ЈtpS4Ј)] (4),
[Ru(CO)(PPh3)(ЈtpS4Ј)] (6), and [Ru(Cl)2(PPh3)(ЈtpS2-
(NH2)2Ј)] (9) were also determined by X-ray diffraction.
Characteristic IR absorptions of the nitro compound 1
are ν(NO) bands of the asymmetric and symmetric ν(NO)
vibrations at 1511, 1333, and 1303 cmϪ1. The ЈtpS4Ј-H2 li-
gand (3) exhibits a medium intensity ν(SH) band at 2526
cmϪ1. All [M(ЈtpS4Ј)] complexes show a nearly identical IR
pattern for the [M(ЈtpS4Ј)] cores. Strong ν(CO) (1965 cmϪ1
)
and ν(SO) (1087 cmϪ1) bands are suited to readily identify
[Ru(CO)(PPh3)(ЈtpS4Ј)] (6) and [Ru(DMSO)(PPh3)(ЈtpS4Ј)]
(7). The ν(SO) band of 7 indicates S-bound DMSO.[12a]
A major concern was the coordination mode of the
ЈtpS4Ј2Ϫ ligand and the question whether, despite of the ri-
gid phenylene bridge, [M(ЈtpS4Ј)] cores assume the same
helical configuration as [M(ЈS4Ј)] cores. Formulas A and B
schematically show the two potential configurations of
[M(ЈtpS4Ј)] cores.
The X-ray structure analysis of 4 and 6 revealed that con-
figuration B is assumed. When the [M(ЈtpS4Ј)] cores bind
two different coligands L and LЈ also 13C-NMR spectra
allow to distinguish between A and B.
Identical coligands L ϭ LЈ result in any case either in C2v
(formula A) or in C2 symmetrical structures (formula B).
When L ϶ LЈ, formula A exhibits (approximately) CS sym-
metry, formula B, however, C1 symmetry. Consequently, in
complexes assuming the structure B, all aromatic C atoms
are chemically non equivalent. The 13C-NMR spectrum of
[Ru(CO)(PPh3)(ЈtpS4Ј)] (6) exhibits 22 aromatic 13C signals
and thus allows to unambiguously assign structure B. In
contrast, the 13C-NMR spectrum of 4 exhibits only 9 aro-
matic 13C signals which do not allow to distinguish between
structures A and B.
Figure 1. Molecular structures of (a) ЈtpS2(NO2)2Ј (1), (b)
ЈtpS2(NH2)2Ј (2), (c) [Ru(Cl)2(PPh3)(ЈtpS2(NH2)2Ј)] (9), (d) [Ru-
(PEt3)2(ЈtpS4Ј)]
· 0.5 Et2O (4 · 0.5 Et2O), and (e) [Ru-
(CO)(PPh3)(ЈtpS4Ј)] · CH2Cl2 (6 · CH2Cl2) (50% probability ellips-
oids, H atoms and solvent molecules omitted)
The coordination of ЈtpS2(NH2)2Ј (2) in [Ru(Cl)2(PPh3)-
The compound ЈtpS2(NO2)2Ј (1) exhibits crystallograph-
(ЈtpS2(NH2)2Ј)] (9) leaving one amino donor dangling could ically imposed C2 symmetry and shows that the two thio-
1
be concluded from the H-NMR spectrum of 9. The pro- ether S atoms lead to a helical preorganization of the three
Eur. J. Inorg. Chem. 1999, 333Ϫ339
335

D. Sellmann, K. Engl, T. Gottschalk-Gaudig, F. W. Heinemann
FULL PAPER
Table 1. Selected distances [pm] and angles [°] of ЈtpS2(NO2)2Ј (1), ЈtpS2(NH2)2Ј (2), [Ru(Cl)2(PPh3)(ЈtpS2(NH2)2Ј)] (9), [Ru(PEt3)2(ЈtpS4Ј)]
· 0.5 Et2O (4 · 0.5 Et2O), and [Ru(CO)(PPh3)(ЈtpS4Ј)] · CH2Cl2 (6 · CH2Cl2)
1
2
S1ϪC15
177.7(2)
178.5(2)
145.8(3)
122.4(2)
123.3(2)
100.93(8)
120.7(2)
122.7(2)
S12ϪC111
S12ϪC120
N11ϪC110
Ϫ
177.0(5)
177.1(4)
137.9(5)
Ϫ
S22ϪC211
S22ϪC220
N21ϪC210
Ϫ
177.8(5)
177.4(4)
136.8(5)
Ϫ
S1ϪC16
N1ϪC10
N1ϪO1
N1ϪO2
Ϫ
Ϫ
Ϫ
Ϫ
C15ϪS1ϪC16
C15ϪC10ϪN1
O1ϪN1ϪO2
C111ϪS12ϪC120
C111ϪC110ϪN11
103.1(2)
122.9(6)
C211ϪS22ϪC220
C211ϪC210ϪN21
104.1(2)
122.6(6)
9
4 · 0.5 Et2O
6 · CH2Cl2
Ru1ϪCl1
Ru1ϪCl2
Ru1ϪS1
Ru1ϪS2
Ru1ϪN1
Ru1ϪP1
Ϫ
S1ϪRu1ϪS2
Cl1ϪRu1ϪS1
Cl2ϪRu1ϪS2
Ϫ
243.8(2)
Ru1ϪS1
239.2(3)
236.1(2)
234.3(2)
239.0(3)
233.0(3)
234.1(3)
Ϫ
173.2(1)
86.81(8)
94.2(1)
Ϫ
241.5(3)
241.8(3)
238.6(3)
238.2(3)
233.8(3)
Ϫ
179.5(11)
172.4(1)
86.4(1)
Ϫ
242.9(2)
227.9(1)
228.9(1)
216.3(3)
230.6(1)
Ϫ
Ru1ϪS2
Ru1ϪS3
Ru1ϪS4
Ru1ϪP1
Ru1ϪP2
Ru1ϪC1
88.54(5)
91.97(5)
88.59(5)
Ϫ
173.4(1)
Ϫ
S1ϪRu1ϪS4
S2ϪRu1ϪS3
P1ϪRu1ϪP2
P1ϪRu1ϪC1
S1ϪRu1ϪP1
S1ϪRu1ϪC1
90.2(3)
Ϫ
95.9(3)
N1ϪRu1ϪP1
Ϫ
90.9(1)
Ϫ
phenylene units as found in 4 and 6. The NO2 groups bind
approximately coplanar to the phenylene rings. Distances [Ru(ЈtpS4Ј)] cores thus is the central five-membered chelate
and angles show no anomalies. ring formed by the metal, the two thioether donors and the
The only significant difference between [Ru(ЈS4Ј)] and
The thioetheramine compound ЈtpS2(NH2)2Ј crystallizes C2H4 or C6H4 bridge. In [Ru(ЈS4Ј)] cores, this chelate ring
with 2 independent molecules per asymmetric unit, having invariably assumes the chair conformation C, in both
practically identical distances and angles. The thioether dis- [Ru(ЈtpS4Ј)] complexes it is found to be virtually planar (D).
tances and angles compare with those of 1, and 2 is also The deviation of the two phenylene C atoms from the plane
characterized by well-approximated C2 symmetry.
defined by the Ru and the two S atoms is only 7(1) pm
The metal centers of all three ruthenium complexes exhi- and 12(1) pm in 4 · 0.5 Et2O and 7(1) and 11(1) pm in 6 ·
bit pseudo-octahedral coordination. The molecular struc- CH2Cl2 respectively.
ture of 9 unambiguously shows that one NH2 group re-
mains uncoordinated. Distances and angles of 9 lie in the
same range as found in other RuII thioether ammine
complexes, for example, [Ru(Br)(PPh3)(ЈBz2S2N2H2Ј)]Br
(ЈBz2S2N2H2Ј ϭ 1,10-dibenzyl-2,3,8,9-dibenzo-1,10-dithia-
4,7-diazadecane).[12b]
The ЈtpS4Ј2Ϫ ligand in 4 and 6 coordinates in the same
helical configuration as the ЈS4Ј2Ϫ ligand in analogous
[Ru(ЈS4Ј)] complexes. As a result, the thiolate donors as-
sume trans positions. Also worth being noted is that the
distances of 4 and 6 are virtually identical to those found
Concluding Discussion
in the analogous [Ru(PR3)2(ЈS4Ј)][1d] or [Ru(L)(PR3)(ЈS4Ј)]
complexes (L ϭ Cl, I).[13] For example, C2-symmetrical
Aim of this work was the synthesis of a tetradentate thio-
[Ru(PnBu3)2(ЈS4Ј)] exhibits RuϪS(thiolate) [239.8(2) pm] ether thiolate ligand which shows a coordination chemistry
and RuϪS(thioether) [236.8(2) pm] distances.[1d] This sug- as rich as that of the ЈS4Ј2Ϫ ligand but is stable toward the
gests that the small difference in the RuϪS(thioether) dis- reductive elimination of the C2 bridge connecting the
tances of 4 [236.1(2) pm; 234.3(2) pm] is due to crystal C6H4S2 units. The new ligand ЈtpS4Ј2Ϫ coordinates to metal
packing effects. It is further noted that the differences either centers in six-coordinate complexes in the same way as the
in the RuϪS(thiolate) or the RuϪS(thioether) distances of ЈS4Ј2Ϫ ligand. The resulting [M(ЈtpS4Ј)] cores exhibit two
C1-symmetrical 6 remain very small and are certainly due trans-positioned thiolate donors and two cis positions
to coligand effects.
which can be occupied by ligands such as PEt3, PPh3, CO,
336
Eur. J. Inorg. Chem. 1999, 333Ϫ339

Transition Metal Complexes with Sulfur Ligands, 134
FULL PAPER
149.32, 137.25, 135.49, 131.42, 128.01, 126.73, 118.94, 115.69,
or DMSO. Orienting experiments indicate that, for ex-
ample, [Ru(PPh3)2(ЈtpS4Ј)] shows a PPh3 substitution chem-
istry similar to that of [Ru(PPh3)2(ЈS4Ј)]. X-ray structure
analyses further demonstrate that the RuS4 distances and
core angles remain invariant when the C2H4 bridge in
[Ru(ЈS4Ј)] is replaced by a phenylene bridge in [Ru (ЈtpS4Ј)].
The only and significant difference of [Ru(ЈS4Ј)] and
[Ru(ЈtpS4Ј)] fragments is the central [RuS2C2] chelate ring,
which is virtually planar in [Ru(ЈtpS4Ј)], but exhibits a chair
conformation in [Ru(ЈS4Ј)]. The stability of the ЈtpS4Ј2Ϫ li-
gand toward reductive cleavage could be demonstrated by
the synthesis of [Os(PEt3)2(ЈtpS4Ј)] (8). Complex 8 is stable
in solution for unlimited periods of time and thus contrasts
[Os(PEt3)2(ЈS4Ј)] which readily eliminates ethylene.
114.69 [C(aryl)]. Ϫ FD MS (CH2Cl2); m/z: 324 [ЈtpS2(NH2)2Ј]ϩ.
Synthesis of Crude ЈtpS4Ј-H2 (3): At 0°C, ЈtpS2(NH2)2Ј (2) (3.0 g,
18.5 mmol) was suspended in a mixture of H2SO4 (2.2 g, 22.4
mmol) and H2O (35 mL). After addition of ice (12 g), a solution
of NaNO2 (1.34 g, 19.4 mmol) in H2O (12 mL) was added dropwise
to the suspension. The resulting yellow suspension was stirred for
1 h at 0°C and subsequently added slowly to a hot solution (85°C)
of KSC(S)OEt (12.0 g, 74.9 mmol) in H2O (30 mL), whereupon a
red oil separated. The mixture was stirred for 45 min at 85°C,
cooled to room temperature, and extracted with CH2Cl2 (150 mL).
The CH2Cl2 extract was evaporated in vacuo. The remaining red
oil was dissolved in EtOH (50 mL), solid KOH (6.0 g) was added,
and the mixture was heated under reflux for 12 h. Evaporation of
the solvent yielded a yellow residue which was suspended in H2O
(100 mL) and extracted with CH2Cl2 (75 mL). To the remaining
aqueous solution hydrochloric acid was added until pH ϭ 1 was
reached and an orange oil separated. The oil was extracted from
the aqueous phase with CH2Cl2 (125 mL), and the CH2Cl2 extract
was dried with Na2SO4. Removal of CH2Cl2 yielded a brown oil.
Experimental Section
General Methods: Unless noted otherwise, all reactions and oper-
ations were carried out under nitrogen using standard Schlenk
techniques. Solvents were dried and distilled before use. As far as
possible, reactions were monitored by IR or NMR spectroscopy. Ϫ
Spectra were recorded with the following instruments: IR (KBr
discs or CaF2 cuvettes, solvent bands were compensated): Perkin
Elmer 983, 1620 FT IR, and 16PC FT-IR. Ϫ NMR: Jeol FT-JNM-
GX 270, EX 270, and Lambda LA 400 with the protio-solvent
signal used as a reference. Chemical shifts are quoted on the δ scale
(downfield shifts are positive) related to tetramethylsilane
(1H, 13C{1H} NMR) or 85% H3PO4 (31P{1H} NMR). Spectra were
recorded at 25°C. Ϫ Mass spectra: Varian MAT 212 and Jeol
MSTATION 700 spectrometers. Ϫ Elemental analysis: Carlo Erba
1
Yield: 1.5 g of 3 (46%). Ϫ IR (Film): ν˜ ϭ 2526 cmϪ1 (SH). Ϫ H
NMR (269.6 MHz, CD2Cl2): δ ϭ 7.40 (m, 2 H, C6H4), 7.30 (m, 2
H, C6H4), 7.35Ϫ6.95 (m, 8 H, C6H4), 4.20 (s, 2 H, SH). Ϫ 13C{1H}
NMR (67.7 MHz, CD2Cl2): δ ϭ 137.43, 135.94, 134.54, 131.42,
130.67, 130.04, 129.32, 128.05, 126.71 [C(aryl)]. Ϫ FD MS
(CH2Cl2); m/z: 358 [ЈtpS4Ј-H2]ϩ.
Purification of Crude ЈtpS4Ј-H2 (3)
[Ni(ЈtpS4Ј)]2: The brown oil containing crude ЈtpS4Ј-H2 (1.5 g, 4.2
mmol) was dissolved in THF (40mL). LiOMe (8.4 mL, 8.4 mmol
of a 1  solution in MeOH) was added and stirred for 1 h. Removal
of the THF yielded a yellow brown solid which turned into a white
powder upon digestion with CH2Cl2 (150 mL). After drying, the
white powder was characterized as Li2ЈtpS4Ј by 1H- and 13C-NMR
spectroscopy. Ϫ Li2ЈtpS4Ј (330 mg, 0.89 mmol) in 20 mL of THF
and Niac2 · 4 H2O (222 mg, 0.89 mmol) in 20 mL MeOH were
combined and stirred for 12 h. A microcrystalline red brown solid
resulted which was separated, washed with MeOH (20 mL), THF
(50 mL), Et2O (20 mL), and dried in vacuo. It analyzed as
EA 1106 or
1108 analyzer.
Ϫ
[RuCl2(DMSO)4],[14]
[RuCl2(PPh3)3],[15] and o-benzenedithiol (ЈS2Ј-H2)[16] were prepared
as described in the literature, potassiumethylxanthogenate, 1-
fluoro-2-nitrobenzene, LiOMe, and nBuLi (2.5  in n-hexane) were
purchased from Aldrich.
ЈtpS2(NO2)2Ј (1): A red-orange solution containing NaOMe (2.70
g, 50 mmol), ЈS2Ј-H2 (3 mL, 23.7 mmol), and 1-fluoro-2-nitroben-
zene (5 mL, 47.4 mmol) in MeOH (100 mL) was heated under
reflux for 20 h. A bright yellow solid precipitated that was sepa-
rated, washed with MeOH (100 mL) and H2O (150 mL), and dried
in vacuo. Yield: 9.00 g of 1 (99%). Ϫ C18H12N2O4S2, 1 (384.42):
calcd. C 56.24, H 3.15, N 7.29, S 16.68; found C 56.41, H 3.12, N
7.33, S 16.28. Ϫ IR (KBr): ν˜ ϭ 1511, 1333, 1303 cmϪ1 ν(NO). Ϫ
1H NMR (269.6 MHz, CD2Cl2): δ ϭ 8.20 (m, 2 H, C6H4),
7.70Ϫ7.20 (m, 8 H, C6H4), 6.90 (m, 2 H, C6H4). Ϫ 13C{1H} NMR
(67.7 MHz, CD2Cl2): δ ϭ 137.52, 137.10, 136.55, 133.57, 131.15,
129.39, 129.35, 125.96, 125.78 [C(aryl)]. Ϫ EI MS (70 eV); m/z:
385 [ЈtpS2(NO2)2Ј]ϩ.
[Ni(ЈtpS4Ј)]2 · THF · 0.5 MeOH. Yield: 290mg (70%).
Ϫ
C40.5H34O1.5S8Ni2 (918.60): calcd. C 52.95, H 3.74, S 27.92; found
C 52.98, H 3.64, S 27.93.
ЈtpS4Ј-H2 (3): A red brown suspension of [Ni(ЈtpS4Ј)]2 · THF · 0.5
MeOH (280 mg, 0.30 mmol) in CH2Cl2 (15 mL) was combined
with concentrated aqueous hydrochlorid acid (10 mL) and stirred
for 1 h. A colorless CH2Cl2 and a light-green aqueous phase
formed. The CH2Cl2 phase was separated, dried with Na2SO4, and
concentrated to dryness, yielding a colorless oil of 3. Yield: 120 mg
of 3 (56%).Ϫ C18H14S4, 3 (358.55): calcd. C 60.30, H 3.94, S 35.77;
found C 60.51, H 3.99, S 35.47.
ЈtpS2(NH2)2Ј (2): A yellow-grey suspension of 1 (6.0 g, 15.6 mmol),
zinc powder (15.4 g, 235.5 mmol), and NH4Cl (8.0 g, 149.6 mmol)
in THF (120 mL) was heated under reflux for 20 h yielding a grey
suspension. The grey solid was filtered off and washed with hot
THF (100 mL), the colorless filtrate was concentrated to dryness.
[Ru(PEt3)2(ЈtpS4Ј)] (4): A yellow suspension of ЈtpS4Ј-H2 (3) (120
mg, 0.33 mmol), NaOMe (38 mg, 0.7 mmol), and
[Ru(Cl)2(DMSO)4] (161 mg, 0.33 mmol) in MeOH (10 mL) was
combined with PEt3 (0.23 mL, 1.69 mmol) and heated under reflux
for 1 h. After cooling to room temperature, the precipitated yellow
The remaining oily residue was recrystallized from hot EtOH (20 solid was separated, washed with MeOH (10 mL) and Et2O (10
mL) yielding white crystals that were washed with EtOH (15 mL)
and dried in vacuo. Yield: 4.00 g of 2 (79%). Ϫ C18H16N2S2, 2
(324.46): calcd. C 66.63, H 4.97, N 8.63, S 19.76; found C 66.67,
H 5.21, N 8.65, S 19.37. Ϫ IR (KBr): ν˜ ϭ 3448, 3360 cmϪ1 ν(NH).
Ϫ H NMR (269.6 MHz, CD2Cl2): δ ϭ 7.45 (m, 2 H, C6H4), 7.25
(m, 2 H, C6H4), 6.95 (m, 2 H, C6H4), 6.80Ϫ6.70 (m, 6 H, C6H4),
4.35 (s, 4 H, NH2). Ϫ 13C{1H} NMR (67.7 MHz, CD2Cl2): δ ϭ 49.75, H 5.89, S 17.42; found C 49.70, H 6.26, S 17.13. Ϫ IR (KBr):
mL), dried in vacuo for 5 min, and redissolved in CH2Cl2 (5 mL).
The yellow CH2Cl2 solution was layered with MeOH (15 mL) and
stored at room temperature. In the course of 4 d, yellow crystals
precipitated that were separated, washed with MeOH (10 mL) and
Et2O (10 mL), and dried in vacuo. Yield: 100 mg of 4 · 0.5 CH2Cl2
(41%). Ϫ C30.5H43ClP2RuS4, 4 · 0.5 CH2Cl2 (736.41): calcd. C
1
Eur. J. Inorg. Chem. 1999, 333Ϫ339
337

D. Sellmann, K. Engl, T. Gottschalk-Gaudig, F. W. Heinemann
FULL PAPER
1
ν˜ ϭ 1086 cmϪ1 δ(PCH). Ϫ H NMR (269.6 MHz, CD2Cl2): δ ϭ
7.90 (m, 2 H, C6H4), 7.75 (m, 2 H, C6H4), 7.30 (m, 2 H, C6H4),
7.20 (m, 2 H, C6H4), 6.90Ϫ6.70 (m, 4 H, C6H4), 1.85 (m, 12 H,
PCH2), 1.05 (m, 18 H, CH3). Ϫ 13C{1H} NMR (67.7 MHz,
CD2Cl2): δ ϭ 159.02, 138.48, 136.66, 132.00, 131.58, 130.10,
CH2Cl2 (15 mL) for 3 h. A yellow solution resulted which was
stirred for another 12 h under CO, reduced in volume to 3 mL,
and layered with MeOH (50 mL). In the course of 3 d, yellow
crystals precipitated which were separated, washed with MeOH (20
mL) and Et2O (10 mL), and dried in vacuo. Yield: 85 mg of 6
129.68, 128.81, 121.06 [C(aryl)], 19.23 (vt, PCH2CH3), 8.49 (73%). Ϫ C37H27OPRuS4, 6 (747.90): calcd. C 59.42, H 3.64, S
(PCH2CH3). Ϫ 31P{1H} NMR (109.38 MHz, CD2Cl2): δ ϭ 18.5
(s). Ϫ FD MS (CH2Cl2, 102Ru); m/z: 694 [Ru(PEt3)2(ЈtpS4Ј)]ϩ.
17.15; found C 59.43, H 3.80, S 16.83. Ϫ IR (KBr): ν˜ ϭ 1964 cmϪ1
(CO). Ϫ 1H NMR (269.6 MHz, CD2Cl2): δ ϭ 7.90 (m, 1 H, C6H4),
7.75 (m, 1 H, C6H4), 7.60 (m, 7 H, C6H4), 7.35 (m, 10 H, C6H4),
7.20 (m, 2 H, C6H4), 7.10Ϫ6.85 (m, 4 H, C6H4), 6.70 (m, 1 H,
C6H4), 6.55 (m, 1 H, C6H4). Ϫ 13C{1H} NMR (100.40 MHz,
CD2Cl2): δ ϭ 200.81 (d, CO); 155.89 (d), 155.28, 138.57 (d), 136.20
(d), 135.36 (d), 134.45 (d), 134.07, 133.09, 132.93 (d), 132.80,
132.62, 131.86, 131.80 (d), 130.83, 130.52 (t), 130.30, 130.19,
129.81, 129.15, 128.16 (d), 122.60, 122.01 [C(aryl)]. Ϫ 31P{1H}
NMR (161.70 MHz, CD2Cl2): δ ϭ 38.98 (s). Ϫ FD MS (CH2Cl2,
102Ru); m/z: 748 [Ru(CO)(PPh3)(ЈtpS4Ј)]ϩ.
[Ru(PPh3)2(ЈtpS4Ј)] (5): A yellow solution of ЈtpS4Ј-H2 (3) (102 mg,
0.28 mmol) in THF (15 mL) was combined with nBuLi (0.23 mL,
0.58 mmol) at Ϫ78°C and subsequently warmed to room tempera-
ture. Addition of [Ru(Cl)2(PPh3)3] (281 mg, 0.28 mmol) resulted in
an orange solution which was stirred for 4 h at room temperature,
heated to reflux for 5 min, and cooled to room temperature. Yellow
microcrystals precipitated which were separated, washed with THF
(20 mL) and Et2O (10 mL), dried in vacuo for 5 min, and redis-
solved in CH2Cl2 (15 mL). The yellow CH2Cl2 solution was fil-
tered, THF (50 mL) was added to the filtrate, and the mixture was
reduced in volume to 10 mL. The precipitated yellow microcrystals
were separated, washed with THF (20 mL), MeOH (20 mL), and
Et2O (20 mL), and dried in vacuo. Yield: 145 mg of 5 · 0.25 CH2Cl2
(51%). Ϫ C54.25H42.5Cl0.5P2RuS4, 5 · 0.25 CH2Cl2 (1003.44): calcd.
C 64.94, H 4.27, S 12.78; found C 65.18, H 4.42, S 12.55. Ϫ 1H
NMR (269.6 MHz, CD2Cl2): δ ϭ 7.60 (m, 2 H, C6H4), 7.30 (m, 14
H, C6H4), 7.25 (m, 6 H, C6H4), 7.15 (m, 2 H, C6H4), 7.05 (m, 14
H, C6H4), 6.85 (m, 2 H, C6H4), 6.60 (m, 2 H, C6H4). Ϫ 13C{1H}
NMR (67.9 MHz, CD2Cl2): δ ϭ 157.70, 138.50, 137.35, 135.20,
131.45, 130.90, 129.80, 129.60, 129.40, 128.95, 128.25, 121.40 [C(a-
ryl)]. Ϫ 31P{1H} NMR (109.38, CD2Cl2) δ ϭ 27.0 (s). Ϫ FD MS
(CH2Cl2, 102Ru); m/z: 982 [Ru(PPh3)2(ЈtpS4Ј)]ϩ.
[Ru(DMSO)(PPh3)(ЈtpS4Ј)] (7): [Ru(PPh3)2(ЈtpS4Ј)] (5) (170 mg,
0.17 mmol) was dissolved in warm DMSO (6 mL, 40°C) and the
resulting yellow solution was cooled to room temperature. After
addition of MeOH (45 mL), a yellow solid precipitated which was
separated, washed with MeOH (50 mL) and Et2O (20 mL), and
dried in vacuo. Yield: 105 mg of 7 (77%). Ϫ C38H33OPRuS5, 7
(798.02): calcd. C 57.19, H 4.17, S 20.09; found C 57.12, H 4.10, S
20.01. Ϫ IR (KBr): ν˜ ϭ 1087 cmϪ1 (SO). Ϫ 1H NMR (269.6 MHz,
CD2Cl2): δ ϭ 7.95 (m, 1 H, C6H4), 7.80Ϫ7.50 (m, 9 H, C6H4),
7.40Ϫ7.15 (m, 11 H, C6H4), 7.10Ϫ6.95 (m, 2 H, C6H4), 6.90Ϫ6.70
(m, 3 H, C6H4), 6.50 (m, 1 H, C6H4), 3.00 (s, 3 H, CH3), 2.70 (s, 3
H, CH3). Ϫ 13C{1H} NMR (67.9 MHz, CD2Cl2): δ ϭ 157.20 (d),
155.03, 137.79 (t), 135.25, 135.00 (d), 134.62, 132.36, 132.20,
132.10, 131.84, 131.44, 130.95, 130.79, 130.47, 130.12, 129.92,
129.54, 129.14, 128.93, 128.75, 127.40 (d), 122.17, 121.63 [C(aryl)],
[Ru(CO)(PPh3)(ЈtpS4Ј)] (6): CO gas was bubbled through a yellow
suspension of [Ru(PPh3)2(ЈtpS4Ј)] (5) (147 mg, 0.15 mmol) in
Table 2. Selected crystallographic data of ЈtpS2(NO2)2Ј (1), ЈtpS2(NH2)2Ј (2), [Ru(Cl)2(PPh3)(ЈtpS2(NH2)2Ј)] (9), [Ru(PEt3)2(ЈtpS4Ј)] · 0.5
Et2O (4 · 0.5 Et2O), and [Ru(CO)(PPh3)(ЈtpS4Ј)] · CH2Cl2 (6 · CH2Cl2)
Compound
1
2
9
4 · 0.5 Et2O
6 · CH2Cl2
formula
Mr[g/mol]
crystal size [mm]
F(000)
C18H12N2O4S2
384.42
C18H16N2S2
324.45
C36H31Cl2N2PRuS2
758.69
C32H47O0.5P2RuS4
1461.89
0.7 ϫ 0.5 ϫ 0.4
3048
C38H29Cl2OPRuS4
832.79
0.6 ϫ 0.5 ϫ 0.4
792
0.40 ϫ 0.30 ϫ 0.25
680
0.6 ϫ 0.6 ϫ 0.6
1544
0.5 ϫ 0.4 ϫ 0.2
1688
space group
crystal system
a [pm]
Pccn
PϪ1
triclinic
P21/n
Pna21
P21/c
orthorhombic
2210.3(12)
518.6(3)
1481.0(4)
90
monoclinic
940.8(6)
1877.4(6)
1866.7(6)
90
orthorhombic
3073.7(4)
1511.0(2)
1491.8(2)
90
monoclinic
1802.3(5)
1142.6(5)
1888.3(4)
90
1101.9(3)
1105.4(3)
1519.1(5)
109.65(2)
105.88(2)
90.22(2)
1.6667(8)
4
b [pm]
c [pm]
α [°]
β [°]
90
90
98.62(4)
90
90
90
110.70(2)
90
γ [°]
V [nm3]
Z
1.698(1)
4
3.260(3)
4
6.929(2)
8
3.638(2)
4
Dcalcd. [g/cm3]
1.504
0.341
1.293
0.317
Nicolet R3m/V
1.546
0.852
1.401
0.808
1.521
0.882
µ [mmϪ1
]
diffractometer
radiation [pm]
temperature [K]
scan technique
2Θrange [°]
Nicolet R3m/V
Siemens P4
Siemens P4
Siemens P4
Mo-Kα (λ ϭ 71.073) Mo-Kα (λ ϭ 71.073) Mo-Kα (λ ϭ 71.073) Mo-Kα (λ ϭ 71.073) Mo-Kα (λ ϭ 71.073)
293
298
200
200
ω scan
4Ϫ55
200
ω scan
4Ϫ52
ω scan
3Ϫ54
3.0Ϫ15.0
3847
ω scan
3Ϫ54
10
ω scan
4Ϫ54
3.0Ϫ30.0
9382
scan speed [°/min]
meas. reflections
indep. reflections
Rint [%]
3.0Ϫ30.0
9870
30.0 (fixed)
8666
8111
1825
7272
7105
8870
7132
3.85
7.53
5.42
4.21
13.12
obs. reflections
σ criterion
1271
1270
5499
6068
2190
Fo > 4σ (Fo)
3.70; 9.59
142
Fo > 4σ (Fo)
3.95; 7.76
397
Fo > 4σ (Fo)
3.59; 12.56
521
Fo > 4σ (Fo)
5.70; 16.41
726
Fo > 4σ (Fo)
6.38; 15.32
424
R1; wR2 [%]
ref. parameters
abs. struct. param.[19]
Ϫ
Ϫ
Ϫ
Ϫ0.03(5)
Ϫ
338
Eur. J. Inorg. Chem. 1999, 333Ϫ339

Transition Metal Complexes with Sulfur Ligands, 134
49.78, 44.52 (SCH3). Ϫ 31P{1H} NMR (109.38 MHz, CD2Cl2): δ ϭ isotropic displacement parameter (2). In the case of 4 and 6 the
FULL PAPER
34.8 (s).
hydrogen atoms were geometrically positioned with isotropic dis-
placement parameters fixed at 1.5 times U(eq) of the preceding
carbon atom. In the case of 2 and 4, there are two crystallograph-
ically independent molecules per asymmetric unit. Selected crystal-
lographic data are summarized in Table 2.[18]
[Os(PEt3)2(ЈtpS4Ј)] (8): A solution of ЈtpS4Ј-H2 (3) (190 mg, 0.53
mmol) and LiOMe (40 mg, 1.06 mmol) in THF (20 mL) was stirred
for 1 h. Removal of the solvent yielded a yellow residue. It was
dissolved in MeOH (20 mL) and combined with OsCl3 · x H2O
(158 mg, 0.53 mmol) and PEt3 (1.60 mL, 11.8 mmol). The resulting
yellow-brown solution was heated under reflux for 2 h, cooled to
room temperature, reduced in volume to 10 mL, and Et2O (10 mL)
was added. A yellow solid precipitated, which was separated,
washed with MeOH (15 mL), Et2O (5 mL), and H2O (10 mL), and
dried in vacuo. Yield: 20 mg of 8 · 2 H2O (5%). Ϫ C30H46O2OsP2S4,
8 · 2 H2O (819.08): calcd. C 43.99, H 5.66, S 15.66; found C 44.27,
Acknowledgments
Support of these investigations by the Deutsche Forschungsgemein-
schaft and Fonds der Chemischen Industrie is gratefully acknowl-
edged.
1
H 5.53, S 15.63. Ϫ H NMR (269.6 MHz, CD2Cl2): δ ϭ 7.90 (m,
[1]
[1a] D. Sellmann, H.-E. Jonk, H.-R. Pfeil, G. Huttner, J. v. Sey-
2 H, C6H4), 7.85 (m, 2 H, C6H4), 7.20 (m, 4 H, C6H4), 6.85 (m, 2
H, C6H4), 6.55 (m, 2 H, C6H4), 1.95 (m, 12 H, PCH2), 1.00 (m, 18
H, CH2CH3). Ϫ 13C{1H} NMR (67.9 MHz, CD2Cl2): δ ϭ 158.98
(d), 139.35, 137.75, 131.54, 131.29, 130.02, 129.90, 129.62, 128.99,
121.26 [C(aryl)], 18.95 (vq, PCH2CH3), 8.51 (PCH2CH3). Ϫ
31P{1H} NMR (109.38 MHz, CD2Cl2): δ ϭ Ϫ25.0 (s). Ϫ FD MS
(CH2Cl2, 192Os); m/z: 784 [Os(PEt3)2(ЈtpS4Ј)]ϩ.
[1b]
erl, J. Organometal. Chem. 1980, 191, 171Ϫ179. Ϫ
D.
Sellmann, H. Friedrich, F. Knoch, M. Moll, Z. Naturforsch.
[1c]
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D. Sellmann, E. Böhlen, Z. Natur-
[1d]
forsch. 1982, 37b, 1026Ϫ1033. Ϫ
D. Sellmann, T. Gott-
schalk-Gaudig, F. W. Heinemann, F. Knoch, Chem. Ber. 1997,
130, 571Ϫ579. Ϫ [1e] D. Sellmann, A. C. Hennige, F. W. Heine-
mann, Eur. J. Inorg. Chem. 1998, 819Ϫ826. Ϫ [1f] D. Sellmann,
B. Seubert, W. Kern, F. Knoch, M. Moll, Z. Naturforsch. 1991,
46b, 1435Ϫ1448. Ϫ [1g] D. Sellmann, H.-J. Kremitzl, F. Knoch,
[Ru(Cl)2(PPh3)(ЈtpS2(NH2)2Ј)] (9): ЈtpS2(NH2)2Ј (2) (168 mg, 0.52
mmol) was added to a brown solution of [Ru(Cl)2(PPh3)3] (495 mg,
0.52 mmol) in THF (25 mL). An orange solution formed which
was heated under reflux for 1 h, cooled to room temperature, and
reduced in volume to 15 mL. Yellow microcrystals precipitated
which were separated, washed with THF (15 mL) and Et2O (25
mL), and dried in vacuo. Yield: 330 mg of 9 · THF (76%). Ϫ
C40H39Cl2N2OPRuS2, 9 · THF (759.93): calcd. C 57.83, H 4.73, N
3.37, S 7.72; found C 57.90, H 4.64, N 3.37, S 7.45. Ϫ IR (KBr):
ν˜ ϭ 1616 cmϪ1 δ(NH). Ϫ 1H NMR (269.6 MHz, CDCl3): δ ϭ 7.85
(m, 7 H, C6H5), 7.15 (m, 1 H, C6H4), 7.40Ϫ7.05 (m,13 H, C6H4),
7.00 (m, 1 H, C6H4), 6.75 (m, 1 H, C6H4), 6.00 (m, 1 H, NH), 5.95
(m, 1 H, C6H4), 5.00 (s, 2 H, NH), 4.80 (m, 1 H, C6H4), 4.50 (m,
1 H, NH). Ϫ 13C{1H} NMR (67.7 MHz, CDCl3): δ ϭ 148.03,
144.16, 142.12, 139.86, 138.60, 135.90, 135.24, 134.50 (d), 133.38,
132.09, 131.56, 131.50, 131.24, 130.86, 130.45, 129.83, 129.02,
128.22 (d), 119.31, 119.11, 119.03 [C(aryl)]. Ϫ 31P{1H} NMR
(109.38 MHz, CD2Cl2): δ ϭ 43.5 (s). Ϫ FD MS (CH2Cl2, 102Ru);
m/z: 721 [Ru(Cl)(PPh3)(ЈtpS2(NH2)2Ј) Ϫ 2 H]ϩ.
[1h]
M. Moll, J. Biol. Inorg. Chem. 1996, 1, 127Ϫ135. Ϫ
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Sellmann, W. Kern, G. Pöhlmann, F. Knoch, M. Moll, Inorg.
[1i]
Chim. Acta 1991, 185, 155Ϫ162.
Ϫ
D. Sellmann, S.
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1990, 29, 4772Ϫ4778.
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[9]
[10]
[11] [11a]
G. E. Hilbert, T. B. Johnson, J. Am. Chem. Soc. 1929, 51,
X-ray Structure Analyses of ЈtpS2(NO2)2Ј (1), ЈtpS2(NH2)2Ј (2),
[Ru(Cl)2(PPh3)(ЈtpS2(NH2)2Ј)] (9), [Ru(PEt3)2(ЈtpS4Ј)] · 0.5 Et2O (4
· 0.5 Et2O), and [Ru(CO)(PPh3)(ЈtpS4Ј)] · CH2Cl2 (6 · CH2Cl2):
Yellow cubes of 1 crystallized from a hot saturated solution of 1 in
THF upon cooling to room temperature, colorless cubes of 2 from
a satured CHCl3 solution. Orange cubes of 9 formed in the course
of 7 d, when a saturated CH2Cl2 solution of 9 was stored at room
temperature. Yellow plates of 4 and 6 were grown by layering
CH2Cl2 solutions of 4 and 6 with Et2O and MeOH, respectively,
at room temperature. In the case of 4, spontaneous separation of
racemic 4 occured. Both independent molecules present in the
asymmetric unit of 4 · 0.5 Et2O represent the same enantiomer.
Distances and angles of the two independent molecules differ only
marginally. Suitable single crystals were sealed under N2 in glass
capillaries. Data were corrected for Lorentz and polarization ef-
fects, no absorption correction. The structures were solved by direct
methods (SHELXTL 5.03[17]). Full-matrix least-squares refinement
was carried out on F2 (SHELXTL 5.03). All non-hydrogen atoms
were refined anisotropically, the positions of the hydrogen atoms
of 1, 2, and 9 were taken from the difference Fourier map and
were either refined isotropically (1, 9) or kept fixed with a common
1526Ϫ1533. Ϫ [11b] D. S. Tarbell, D. K. Fukushima, Org. Synth.
Coll. Vol. 1951, 3, 809Ϫ811.
[12] [12a]
K. Nakamoto, Infrared Spectra of Inorganic and Coordi-
nation Compounds, 4th ed., Wiley and Sons, New York, 1986,
p. 270. Ϫ [12b] D. Sellmann, R. Ruf, F. Knoch, M. Moll, Inorg.
Chem. 1995, 34, 4745Ϫ4755.
[13]
[14]
[15]
D. Sellmann, T. Gottschalk-Gaudig, F. W. Heinemann, Inorg.
Chim. Acta 1998, 269, 63Ϫ72.
I. P. Evans, A. Spencer, G. Wilkinson, J. Chem. Soc., Dalton
Trans. 1973, 204Ϫ209.
T. A. Stephenson, G. Wilkinson, J. Inorg. Nucl. Chem. 1966,
28, 945Ϫ956.
[16]
[17]
J. Degani, R. Fochi, Synthesis 1976, 7, 471Ϫ472.
SHELXTL 5.03 for Siemens Crystallographic Research Systems,
Siemens Analytical X-ray Instruments Inc., Madison, WI,
U.S.A., 1995.
[18]
Crystallographic data (excluding structure factors) for the struc-
tures reported in this paper have been deposited with the Cam-
bridge Crystallographic Data Centre as CCDC-102376 (1),
-102377 (2), -102378 (4), -102379 (6), -102380 (9). Copies of the
data can be obtained free of charge on application to CCDC,
12 Union Road, Cambridge CB2 1EZ, UK [Fax: int. code ϩ
44-1223/336-033; E-mail: deposit@ccdc.cam.ac.uk].
H. D. Flack, Acta Crystallogr. 1983, A39, 876Ϫ881.
Received August 7, 1998
[19]
[I98268]
Eur. J. Inorg. Chem. 1999, 333Ϫ339
339