Transition metal complexes with sulfur ligands, 135 [(+)] - Electron- rich Fe and Ru complexes with the new trisamine dithiolate ligand 'N3H3S2'-H2-bis(2-mercaptophenylamino)diethylamine]

Article abstract of DOI:10.1002/(sici)1099-0682(19990202)1999:2<341::aid-ejic341>3.0.co;2-v

In order to obtain iron and ruthenium complexes which are analogous to [M(L)('NHS₄')] and [M(L)('N₂H₂S₃')] complexes ['NHS₄'^2- = 2,2'-bis(2- mercaptophenylthio)diethylamine(2-), 'N₂H₂S₃'^2- = 2,2'-bis(2- mercaptophenylamino)diethylsulfide(2-)] but have electron-richer metal centers, the new pentadentate amine thiolate ligand 'N₃H₃S₂'-H₂ [ = 2,2'bis(2-mercaptophenylamino)diethylamine] (4) was synthesized. The dianion 'N₃H₃S₂'^2- reacted with Fe(II) salts to give high-spin [Fe('N₃H₃S₂')] (5) [μ(eff) (293 K) = 3.94 μ(B)], which yielded diamagnetic [Fe(CO)('N₃H₃S₂')] (6) upon reaction with CO. Complex 6 exhibits a low- frequency v(CO) band (1934 cm^-1 in THF) indicating an electron-rich Fe center and a strong Fe-CO bond. In spite of this, 6 readily dissociated in solution to 5 and CO. The reaction of [RuCl₂(PPh₃)₃] with 'N₃H₃S₂'^2- yielded [Ru(PPh₃)('N₃H₃S₂')] (7), which proved inert with respect to PPh₃ substitution but could be methylated at the thiolate donors. The resulting [Ru(PPh₃)('N₃H₃S₂'-Me₂)]I₂ (8) proved as inert towards substitution as 7. Complex 8 could reversibly be deprotonated to give [Ru(PPh₃)('N₃'-H₂S₂'-Me₂)]I (11), in the course of which the [RuPN₃S₂] cores rearrange from C(S) to C₁ symmetry. Reversible protonation/deprotonation was also found with [Ru(NO)('N₃'-H₂S₂')] (9) which formed from [RuCl₃(NO)(PPh₃)₂] and 'N₃H₃S₂'^2- in the presence of one additional equivalent of LiOMe. Protonation of 9 with HBF₄ gave [Ru(NO)('N₃H₃S₂')]BF₄ (10). The NMR spectra and the X-ray structure analysis of 8 proved that the [RuPN₃S₂] cores of 7 and 8 exhibit a Cs- symmetrical meso structure. In all other complexes, however, the [MLN₃S₂] cores exhibit a C₁-symmetrical structure. It results from the fac-mer coordination mode of the 'N₃H₃S₂'^2- ligand and favors the planarization of amide donors when NH functions are reversibly deprotonated.

Full text of DOI:10.1002/(sici)1099-0682(19990202)1999:2<341::aid-ejic341>3.0.co;2-v

FULL PAPER
Transition Metal Complexes with Sulfur Ligands, 135[°]
Electron-Rich Fe and Ru Complexes with the New Trisamine Dithiolate
Ligand ЈN3H3S2Ј-H2 [2,2Ј-Bis(2-mercaptophenylamino)diethylamine]
Dieter Sellmann,*[a] Jürgen Utz,[a] and Frank W. Heinemann[a]
Keywords: N ligands / S ligands / Iron / Ruthenium / Pentadentate ligands
In order to obtain iron and ruthenium complexes which are
analogous to [M(L)(ЈNHS4Ј)] and [M(L)(ЈN2H2S3Ј)] complexes
[ЈNHS4Ј2– = 2,2Ј-bis(2-mercaptophenylthio)diethylamine(2–),
ЈN2H2S3Ј2– = 2,2Ј-bis(2-mercaptophenylamino)diethylsulfide-
(2–)] but have electron-richer metal centers, the new
pentadentate amine thiolate ligand ЈN3H3S2Ј-H2 [ = 2,2Ј-
bis(2-mercaptophenylamino)diethylamine] (4) was synthe-
sized. The dianion ЈN3H3S2Ј2– reacted with FeII salts to give
high-spin [Fe(ЈN3H3S2Ј)] (5) [µeff (293 K) = 3.94 µB], which
yielded diamagnetic [Fe(CO)(ЈN3H3S2Ј)] (6) upon reaction
with CO. Complex 6 exhibits a low-frequency ν(CO) band
(1934 cm–1 in THF) indicating an electron-rich Fe center and
a strong Fe–CO bond. In spite of this, 6 readily dissociated
in solution to 5 and CO. The reaction of [RuCl2(PPh3)3] with
ЈN3H3S2Ј2– yielded [Ru(PPh3)(ЈN3H3S2Ј)] (7), which proved
inert with respect to PPh3 substitution but could be
methylated at the thiolate donors. The resulting
[Ru(PPh3)(ЈN3H3S2Ј-Me2)]I2 (8) proved as inert towards
substitution as 7. Complex could reversibly be
8
deprotonated to give [Ru(PPh3)(ЈN3H2S2Ј-Me2)]I (11), in the
course of which the [RuPN3S2] cores rearrange from CS to
C1 symmetry. Reversible protonation/deprotonation was also
found with [Ru(NO)(ЈN3H2S2Ј)] (9) which formed from
[RuCl3(NO)(PPh3)2] and ЈN3H3S2Ј2– in the presence of one
additional equivalent of LiOMe. Protonation of 9 with HBF4
gave [Ru(NO)(ЈN3H3S2Ј)]BF4 (10). The NMR spectra and the
X-ray structure analysis of 8 proved that the [RuPN3S2] cores
of 7 and 8 exhibit a CS-symmetrical meso structure. In all
other complexes, however, the [MLN3S2] cores exhibit a C1-
symmetrical structure. It results from the fac-mer
coordination mode of the ЈN3H3S2Ј2– ligand and favors the
planarization of amide donors when NH functions are
reversibly deprotonated.
StructureϪfunction relationships of transition metal more labile than [Fe(CO)(ЈNHS4Ј)], and neither N2 nor
complexes are primarily determined by the metal oxidation N2H2, N2H4, or NH3 complexes could be obtained with the
state, type and number of the donor atoms, and the struc- [Fe(ЈN2H2S3Ј)] fragment. Beyond that all [Fe(L)(ЈN2H2S3Ј)]
ture of the metal ligand core.[1] In quest of metal complexes and corresponding [Ru(L)(ЈN2H2S3Ј)] complexes were
that combine structural (metal sulfur sites) and functional shown to exhibit the core structure C having thiolate donor
(reactivity) features of nitrogenase centers, our interest fo- atoms in cis positions. The core structure C distinctly differs
cusses on complexes with multidentate ligands which con- from the [Fe(ЈNHS4Ј)] core structure B having trans-thiolate
tain amine N, thioether S, and thiolate S donors. In this donors. trans-Thiolate donors, however, proved to be essen-
search the [Fe(ЈNHS4Ј)] fragment (Scheme 1) was found to tial for the stabilization of molecules such as N2H2 in [µ-
exist in the diastereomeric forms A and B and to bind N2H2{Fe(ЈNHS4Ј)}2], because only a trans coordination of
N2H2, N2H4, NH3, and CO, but not N2.[2] As high electron thiolate donors allows the formation of strong NϪH···(S)2
densities at the metal centers usually favor the coordination bridges.[2a,2c]
of N2,[3] we tried to increase the iron electron density in the
In the series of systematically varied ligands, our next
[Fe(ЈNHS4Ј)] cores through a systematic substitution of σ- target ligand was ЈN3H3S2Ј-H2. It is comparable with the
donorϪπ-acceptor thioether functions by σ-donor amine ЈNHS4Ј2Ϫ ligand in so far as all thioether donors are ex-
functions.
changed for amine donors. Simultaneously, the terminal thi-
[4]
The first target ligand ЈN2H2S3Ј-H2 yielded the CO olate donors are maintained in a coordination mode that
complex [Fe(CO)(ЈN2H2S3Ј)], whose ν(CO) frequency of enables them to occupy, at least in principle, trans positions
1932 cmϪ1 indicated a higher Fe electron density when in six-coordinate metal complexes.
compared with to that of [Fe(CO)(ЈNHS4Ј)] (1960 cmϪ1).
However, despite the low-frequency ν(CO) indicating strong
FeϪCO π-back-bonding, [Fe(CO)(ЈN2H2S3Ј)] proved much
Results
Ligand Synthesis
[°]
Part 134: D. Sellmann, K. Engl, T. Gottschalk-Gaudig,
As in the case of the ЈN2H2S3Ј2Ϫ ligand synthesis, the
requirement of terminal thiolate functions in the target li-
gand ЈN3H3S2Ј2Ϫ necessitated a specific synthetic route
F. W. Heinemann, Eur. J. Inorg. Chem. 1999, 333Ϫ339
[a]
Institut für Anorganische Chemie der Universität
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, 341Ϫ348
(Scheme 2).
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
1434Ϫ1948/99/0202Ϫ0341 $ 17.50ϩ.50/0
341

D. Sellmann, J. Utz, F. W. Heinemann
FULL PAPER
Scheme 1. Ligands and core structures of metal complex fragments
Scheme 2. Synthesis of ЈN3H3S2Ј-H2 (4)
Alkylation of 2(3H)-benzothiazolone (1) with TsN-
The reaction a) of FeII salts with ЈN3H3S2Ј2Ϫ, which was
(C2H4I)2 in the presence of K2CO3 yielded 2 as major prod- routinely obtained from ЈN3H3S2Ј-H2 and two equivalents
uct. The rather unusual N-lost derivative TsN(C2H4I)2 had of LiOMe, gave grey-white [Fe(ЈN3H3S2Ј)] (5). The struc-
to be applied because all other and more common alky- ture of 5 remains unknown, but in analogy to the closely
lation reagents such as NH(C2H4Br)2 or amides of the type related dinuclear [Fe(ЈN2H2S3Ј)]2 complex, 5 is suggested to
R(CO)N(C2H4Br)2 failed. For example, NH(C2H4Br)2 gave exhibit a dinuclear structure resulting from thiolate bridg-
piperazine derivatives[5] instead of alkylating 1, the amides ing. In solid state, 5 is paramagnetic [µeff (293 K) ϭ 3.94
R(CO)N(C2H4Br)2 rearranged.[6] From the crude product µB]. The µeff value is compatible with four unpaired elec-
of 2, traces of by-products resulting from oxygen alkylation trons per Fe center, which are partially coupled antiferro-
of 1[7] could readily be removed by extraction with EtOH. magnetically through FeϪSϪFe bridges.
Compound 2 is soluble in CH2Cl2 and THF and moder-
All attempts to obtain [Fe(L)(ЈN3H3S2Ј)] derivatives by
ately soluble in EtOH or MeOH; it was characterized by
treating 5 with N2H4, NEt4N3, or PMe3 in MeOH or THF
the usual spectroscopic methods and by elemental analysis.
solutions remained unsuccessful and yielded only the start-
The 13C{1H}-NMR CO signal (δ ϭ 170.6) and the IR
ing complex 5. Exclusively CO could be added to give red
ν(CO) band (1678 cmϪ1 in KBr) are particularly suited to
[Fe(CO)(ЈN3H3S2Ј)] (6) (Scheme 3, reaction b). Complex 6
confirm alkylation of the N atom in 1 and to identify 2.
is diamagnetic and probably exhibits the C1-symmetric
Alkaline hydrolysis of 2 by aqueous NaOH in EtOH and
structure indicated in Scheme 3. The C1 symmetry is con-
subsequent acidification with hydrochloric acid yielded 3 as
cluded from the NMR spectra of 6 (see below), and it corre-
yellow powder in nearly quantitative amounts. The final
sponds with that of the related [Fe(CO)(ЈN2H2S3Ј)] whose
step, the reductive detosylation of the central N atom in 3
structure has been determined by X-ray diffraction. Com-
with sodium in liquid NH3 gave 4, which was isolated after
plex 6 exhibits a low-frequency ν(CO) IR band at 1934
recrystallization from EtOH in form of beige needles.
cmϪ1 (in THF) indicating strong FeϪCO π-back-bonding.
In accordance with this, solid 6 is stable at room tempera-
ture for unlimited periods of time. In solution, however, 6
rather unexpectedly readily loses CO within a few hours
Syntheses of Fe and Ru Complexes
Scheme 3 summarizes the syntheses and reactions of and yields the starting complex 5. In this respect, the
[M(ЈN3H3S2Ј)] complexes.
properties of 6 resemble very closely those of the related
342
Eur. J. Inorg. Chem. 1999, 341Ϫ348

Transition Metal Complexes with Sulfur Ligands, 135
FULL PAPER
Scheme 3. Syntheses and reactions of [M(ЈN3H3S2Ј)] complexes (M ϭ Fe, Ru)
[Fe(CO)(ЈN2H2S3Ј)]. For this reason, we tried to obtain the Me2)]I2 (8) (reaction d), whose molecular structure could
kinetically less labile ruthenium homologue of 6. As in the be determined by X-ray structure analysis.
case of the ЈN2H2S3Ј2Ϫ ligand, all efforts to obtain the cor-
Coordination of the ЈN3H3S2Ј2Ϫ ligand to (nitrosyl)ru-
responding monocarbonyl complex [Ru(CO)(ЈN3H3S2Ј)] re- thenium complexes resulted in deprotonation of one aro-
mained unsuccessful. The composition of the complexes re- matic amine function. Treatment of [RuCl3(NO)(PPh3)2]
sulting from reactions of precursors such as with ЈN3H3S2Ј2Ϫ and LiOMe yielded neutral, deep green
[Ru(H)(Cl)(CO)(PCy3)2][8] or [Ru(Cl)2(CO)3(THF)][9] with [Ru(NO)(ЈN3H2S2Ј)] (9), which exhibits one amide donor
ЈN3H3S2Ј2Ϫ suggested that only four of the five ЈN3H3S2Ј2Ϫ (reaction g). The formation of the amide could further be
donors had become coordinated.
substantiated by protonation of 9 with HBF4 (reaction h).
However, coordination of all five ЈN3H3S2Ј2Ϫ donors It yielded red [Ru(NO)(ЈN3H3S2Ј)]BF4 (10). The pro-
could be achieved when [RuCl2(PPh3)3] was treated with tonation is accompanied by a shift of the ν(NO) band from
ЈN3H3S2Ј2Ϫ in refluxing THF (Scheme 3, reaction c). Yel- 1779 cmϪ1 in 9 to 1855 cmϪ1 in 10. The 1H- and 13C-NMR
low [Ru(PPh3)(ЈN3H3S2Ј)] (7) resulted, which interestingly spectra indicate that 10 exists in two diastereomeric forms
also formed when [RuCl2(PPh3)3] was treated with the N- (see below).
tosylated ligand ЈTsN3H2S2Ј2Ϫ (3). This indicates that coor-
dination of 3 facilitates its detosylation. Detosylation of
amides normally needs much more drastic reaction con-
ditions.[10] The CS symmetry of 7 indicated in Scheme 3 is
concluded from the 1H-NMR signal pattern of the aliphatic
Substitution and Acid؊Base Reactions
The
reactivity
of
the
complexes
containing
ЈN3H3S2Ј2Ϫ protons. It consists of two pseudo triplets and [M(ЈN3H3S2Ј)] or [M(ЈN3H2S2Ј)] cores paralleled that of
a multiplet and characteristically differs from the pattern complexes with [M(ЈN2H2S3Ј)] or [M(ЈN2HS3Ј)] cores. The
observed consisting of two pseudo triplets. This signal pat- [Fe(CO)(ЈN3H3S2Ј)] complex proved unexpectedly labile
tern characteristically differs from that observed for the ali- with respect to CO loss.
phatic protons in C1-symmetrical [Fe(CO)(ЈN3H3S2Ј)]. A
The ruthenium complexes proved extremely inert to-
13C-NMR spectrum confirming this conclusion could not wards substitution. For example, the PPh3 ligand in
be recorded due to insufficient solubility of 7. However, the [Ru(PPh3)(ЈN3H3S2Ј)] (7) could neither be substituted by
CS symmetry assumed for 7 is further supported by the CS- CO (50 bar, 2 d, THF) nor by N2H4 which was used as
symmetrical structure of the S-methylated derivative of 7. solvent (40°C, 1 d). With the intention to labilize the
Alkylation of 7 by CH3I yielded [Ru(PPh3)(ЈN3H3S2Ј- RuϪPPh3 bond by converting the thiolate into thioether
Eur. J. Inorg. Chem. 1999, 341Ϫ348
343

D. Sellmann, J. Utz, F. W. Heinemann
FULL PAPER
functions, 7 was alkylated. The resulting [Ru(PPh3)- Characterization of Complexes
(ЈN3H3S2Ј-Me2)]I2 (8) proved to be as inert towards substi-
All complexes except [Fe(ЈN3H3S2Ј)]2 (5) are diamagnetic
tution as 7.
and exhibit similar solubilities. They are soluble in DMF
and DMSO, moderately soluble in CH2Cl2, THF, and ace-
tone, and virtually insoluble in all other common organic
solvents. The phosphane complex [Ru(PPh3)(ЈN3H3S2Ј)] (7)
is only very moderately soluble even in DMSO. All com-
plexes have been characterized by elemental analysis, IR,
NMR, and mass spectra. The FD mass spectra of the com-
plexes showed the molecular ions except in the case of 6 in
which only the decarbonylated species [Fe(ЈN3H3S2Ј)]ϩ
could be observed. As expected the IR (KBr) spectra show
numerous bands. One broad or up to three weak- to me-
dium-intensity ν(NH) bands in the region of 3293 to 3102
cmϪ1 can be used as an IR probe for the complexes con-
As in the case of [M(ЈN2H2S3Ј)] complexes, protonation-
Ϫdeprotonation reactions of the [M(ЈN3H3S2Ј)] cores could
be observed. Protonation of the amide donor in [Ru-
(NO)(ЈN3H2S2Ј)] yielded two diastereomers of [Ru-
(NO)(ЈN3H3S2Ј)]BF4. The formation of two diastereomers
could be concluded from the 13C{1H}-NMR spectrum and
is explained by the stereogenicity of the amine function that
results from either a “front”- or a “back”-side attack of the
proton upon the prochiral amide donor (Equation 1).
taining [M(ЈN3H3S2Ј)] cores. In
contrast, [Ru-
(NO)(ЈN3H2S2Ј)] (9) containing one amide donor gives rise
to two medium ν(NH) bands at 3245 and 3224 cmϪ1. The
complexes 6, 9, and 10 can further readily be identified by
their strong ν(CO), ν(NO), and ν(BF4) bands which appear
at 1934 cmϪ1 (6 in THF), 1779 cmϪ1 (9 in KBr), and 1855
and 1084 cmϪ1, respectively (10 in KBr). 13C{1H}-NMR
spectra are the most suitable probe for distinguishing be-
tween C1 or CS symmetry of the complexes[4][12]. Twelve
aromatic 13C-NMR signals in the range δ ϭ 160Ϫ108 and
four aliphatic 13C-NMR signals of the N-bonded C atoms
in the range δ ϭ 65Ϫ45 indicate C1 symmetry of the com-
plexes 6 and 9 containing [M(ЈN3H3S2Ј)] or [M(ЈN3H2S2Ј)]
cores. Two sets of this signal pattern in the 13C{1H}-NMR
spectrum of 10 suggest the presence of two diastereomers.
Only six aromatic and two aliphatic (N-bonded C2H4
groups) 13C-NMR signals for the [M(ЈN3H3S2Ј)] core indi-
cate the CS symmetry of 8, which was confirmed by X-ray
structure analysis. The CS symmetry of 8 is also reflected in
The
protonationϪdeprotonation
reactions
of
[Ru(PPh3)(ЈN3H3S2Ј-Me2)]I2 (8) differ from those of the
analogous [Ru(PPh3)(ЈN2H2S3Ј-Me2)]I2. The 1H-NMR
spectrum and X-ray structure determination established
that 8 formed in isomerically pure form as CS-symmetrical
species when synthesized from 7 and CH3I. Complex 8 can
be deprotonated by bases such as N2H4 to give
[Ru(PPh3)(ЈN3H2S2Ј-Me2)]I (11), which is converted into
[Ru(PPh3)(ЈN3H3S2Ј-Me2)](I)(Cl) (12) when treated with
1
the appearance of only one SCH3 singlet in the H-NMR
spectrum.
HCl. The H- and 13C-NMR spectra unambiguously show
1
that 11 and 12 have C1 symmetry only. Thus, the depro-
tonationϪprotonation reactions [steps e) and f) in Scheme
3] lead to a configurational rearrangement of 8.
X-ray Structure Analysis of [Ru(PPh3)(ЈN3H3S2Ј-
Me2)]I2 · 2 CH2Cl2 (8 · 2 CH2Cl2)
The rearrangement could occur via the five-coordinate
intermediate [Ru(PPh3)(ЈN3H2S2Ј-Me2)]ϩ in which one
thioether donor has dissociated. Driving force of this re-
arrangement probably is the planarization tendency of am-
ide N atoms[11] and, in addition, the capability of amide
donors to stabilize five-coordinate intermediates by π dona-
tion.[2e] The rearrangement further indicates that, like
[M(ЈN2H2S3Ј)] cores, also [M(ЈN3H3S2Ј)] cores prefer the
C1-symmetrical configuration. It is noteworthy that the pro-
tonation of 11 yields only one diastereomer of 12 (cf. ref.[4]).
The molecular structure of [Ru(PPh3)(ЈN3H3S2ЈϪMe2)]I2
· 2 CH2Cl2 (8 · 2 CH2Cl2) (Figure 1) was determined by X-
ray structure analysis. Table 1 lists selected distances and
angles.
The ruthenium center of 8 is pseudo-octahedrally sur-
rounded by the phosphane and the ЈN3H3S2Ј-Me2 donors.
Both the aromatic amine and the thioether donor atoms
assume cis positions, and the aliphatic amine donor N3 and
the phosphane donor occupy trans positions such that 8
exhibits approximate CS symmetry. Distances and angles
show no anomalies and are typical for this type of RuII
complexes.[4,13] Within the crystal, the complex cations, iod-
ide anions, and CH2Cl2 solvate molecules are connected by
hydrogen bonds. The shortest interionic contact is observed
between the N2, H2, and I2 atoms [N2ϪH2···I2: N2ϪH2
86(6), N2···I2 352.8(4), H2···I2 274(5) pm; N2ϪH2···I2
153(4)°].
344
Eur. J. Inorg. Chem. 1999, 341Ϫ348

Transition Metal Complexes with Sulfur Ligands, 135
FULL PAPER
an amide donor is their only significant reaction. It has pre-
viously been discussed in detail that this formation of π-
donor amides can lead to either labilization or stabilization
of trans-metalϪligand bonds.[4,14]
Experimental Section
General: Unless noted otherwise, all procedures were carried out
under N2 at room temperature by using Schlenk techniques. Sol-
vents were dried and distilled before use. As far as possible the
reactions were monitored by IR spectroscopy. Ϫ Spectra were re-
corded with the following instruments: IR: Perkin Elmer 16 PC
FT-IR. Ϫ NMR: JEOL JNM-GX 270 and JNM-EX 270 [1H
NMR (269.6 MHz) and 13C NMR (67.7 MHz): The protio-solvent
signal was used as an internal reference. Chemical shifts are quoted
on the δ scale (downfield shifts are positive) relative to tetrameth-
ylsilane; 31P NMR (109.38 MHz): external standard H3PO4]. Ϫ
Mass spectra: Varian MAT 212 and JEOL JMS 700. Ϫ Magnetic
moments: Johnson Matthey magnetic susceptibility balance
(293K). Ϫ [RuCl3(NO)(PPh3)2],[15] [RuCl2(PPh3)3],[16] N,N-bis[2-(p-
tolylsulfonyloxy)ethyl]-p-toluolsulfonamide,[17] and 2(3H)-benzo-
thiazolone[18] were prepared by literature methods. N,N-bis(2-iodo-
ethyl)-p-toluenesulfonamide[19] was prepared in situ and directly
used afterwards. Hydrazine was obtained by twofold distillation of
N2H4 · H2O over solid potassium hydroxide under reduced pres-
sure.
Figure 1. Molecular structure of the cation of [Ru(PPh3)(ЈN3H3S2Ј-
Me2)]I2 · 2 CH2Cl2 (8 · 2 CH2Cl2) (50% probability ellipsoids, H
atoms and solvate molecules omitted)
Table 1. Selected distances [pm] and angles [°] of [Ru(PPh3)-
(ЈN3H3S2Ј-Me2)]I2 · 2 CH2Cl2 (8 · 2 CH2Cl2)
Ru1ϪN1
Ru1ϪN2
Ru1ϪN3
Ru1ϪP1
Ru1ϪS1
Ru1ϪS2
217.6(3)
215.9(3)
216.4(3)
234.3(1)
231.5(1)
231.3(1)
N1ϪRu1ϪN3
N2ϪRu1ϪN3
P1ϪRu1ϪN3
S1ϪRu1ϪN3
S2ϪRu1ϪN3
N1ϪRu1ϪN2
80.5(1)
80.6(1)
173.4(1)
96.0(1)
96.2(1)
96.0(1)
Concluding Discussion
Alkylation of 2(3H)-Benzothiazolone (1) with N,N-Bis(2-iodoethyl)-
p-toluenesulfonamide To Give 2: A solution of N,N-bis[2-(p-tolylsul-
fonyloxy)ethyl]-p-toluenesulfonamide (2.03 g, 3.58 mmol) and NaI
(2.50 g, 10.68 mmol) in acetone (40 mL) was refluxed for 14 h
and concentrated to dryness. The resulting residue was dissolved in
CH2Cl2 (30 mL), insoluble material was removed by filtration, and
the filtrate was concentrated to dryness, yielding N,N-bis(2-iodo-
ethyl)-p-toluenesulfonamide (1.52 g, 89%). Ϫ A suspension of
2(3H)-benzothiazolone (0.96 g, 6.35 mmol) and K2CO3 (0.88 g,
In the course of a study aiming at the series of ЈNHS4Ј2Ϫ
,
ЈN2H2S3Ј2Ϫ, and ЈN3H3S2Ј2Ϫ ligands and transition metal
complexes with increasing electron density at the transition
metal centers, the new pentadentate ligand ЈN3H3S2Ј-H2
was prepared.
A special synthetic route which warranted the NH and
the terminal thiolate donors of ЈN3H3S2Ј-H2 was devel-
oped. The low-frequency ν(CO) of [Fe(CO)(ЈN3H3S2Ј)] (6) 6.37 mmol) in 2-butanone (20 mL) was refluxed for 30 min and
(1934 cmϪ1) shows that the iron center indeed exhibits a
then combined with a solution of N,N-bis(2-iodoethyl)-p-toluene-
sulfonamide (1.52 g, 3.17 mmol) in 2-butanone (10 mL). The re-
high electron density. However, the Fe electron density is
sulting white suspension was refluxed for 14 h and concentrated to
not higher than in the related [Fe(CO)(ЈN2H2S3Ј)] (1932
dryness to give a foamy white residue. It was redissolved in EtOH
cmϪ1), the CO ligand is very labile and no small molecules
(30 mL). Addition of water (50 mL) precipitated a white powder,
other than CO could be coordinated to the [Fe(ЈN3H3S2Ј)]
which was separated, digested with EtOH (30 mL), and dried in
fragment. With respect to [Fe(ЈNHS4Ј)] fragments, a further
serious shortcoming of [M(L)(ЈN3H3S2Ј)] complexes is their
core structure. Like [M(L)(ЈN2H2S3Ј)] complexes,
[M(L)(ЈN3H3S2Ј)] complexes appear to prefer C1-symmetri-
vacuo. Yield: 1.39 g (74%). Ϫ C25H23N3O4S3 (525.67): calcd. C
57.12, H 4.41, N 7.99, S 18.30; found C 56.71, H 4.47, N 7.98, S
18.11. Ϫ IR (KBr): ν˜ ϭ 1678 vs ν(CO), 1327, 1153 w ν(SO2) cmϪ1
.
Ϫ MS (FD, CH2Cl2); m/z: 525 [2]ϩ. Ϫ 1H NMR (CDCl3): δ ϭ 7.59
cal structures and thiolate donors in cis position. Only (d, 2 H, C6H4), 7.40 (d, 2 H, C6H4), 7.34 (d, 2 H, C6H4), 7.25Ϫ7.10
(m, 6 H, C6H4), 4.14 (t, 4 H, C2H4), 3.50 (t, 4 H, C2H4), 2.35 (s, 3
H, CH3, Ts). Ϫ 13C{1H} NMR (CDCl3): δ ϭ 170.6 (CO), 144.6,
137.3, 135.8, 130.6, 127.7, 127.4, 124.0, 123.4, 123.3, 111.3 (C,
aryl), 46.9, 42.2 (C2H4), 22.2 (CH3, Ts).
[Ru(PPh3)(ЈN3H3S2Ј)] (7) and its S-methylated derivative
[Ru(PPh3)(ЈN3H3S2ЈϪMe2)]I2 (8) exhibit CS-symmetrical
structures which are comparable with the CS-symmetrical
diastereomer of the [Fe(ЈNHS4Ј)] fragment. However, the
deprotonationϪprotonation reactions of 8 lead to the C1-
symmetrical diastereomer 12 and indicate that also the
[Ru(ЈN3H3S2Ј)] fragment prefers the C1-symmetrical core
structure. Thus, with respect to structure, [M(L)(ЈN3H3S2Ј)]
and [M(L)(ЈN2H2S3Ј)] complexes show largely similar
properties. The same holds for the electronic and reactivity
features. The corresponding carbonyliron complexes exhibit
high electron density at the metal centers, but are labile. The
ruthenium complexes are virtually substitution inert. The
ЈTsN3H2S2Ј-H2 (3): A suspension of 2 (1.83 g, 3.48 mmol) in EtOH
(20 mL) was combined with a solution of NaOH (1.39 g, 34.8
mmol) in H2O (20 mL) and refluxed for 18 h. Concentrated hydro-
chloric acid was added until pH ϭ 3 was reached, the solution was
concentrated in volume to one half, diluted with H2O (60 mL), and
extracted with CH2Cl2 (60 mL). The combined CH2Cl2 phases were
dried with anhydrous Na2SO4 and concentrated to dryness, yield-
ing 3 as a yellow powder. Yield: 1.60 g (97%). Ϫ C23H27N3O2S3
(473.69): calcd. C 58.32, H 5.75, N 8.87, S 20.31; found: C 58.10,
H 5.90, N 8.91, S 19.99. Ϫ IR (KBr): ν˜ ϭ 3385, 3364 w ν(NH),
reversible deprotonation of one amine NH function to give 2522 w ν(SH), 1323 s, 1159 vs ν(SO2) cmϪ1. Ϫ MS (FD, CH2Cl2);
Eur. J. Inorg. Chem. 1999, 341Ϫ348 345

D. Sellmann, J. Utz, F. W. Heinemann
m/z: 474 [ЈTsN3H2S2Ј-H2]ϩ. Ϫ 1H NMR (CDCl3): δ ϭ 7.62 (d, 2 MeOH) in THF (30 mL). The reaction mixture was stirred for 24
FULL PAPER
H, C6H4, Ts, ortho to SO2), 7.23 (d, 2 H, C6H4, ortho to SH), 7.17
(d, 2 H, C6H4, Ts, meta to SO2), 7.03 (dd, 2 H, C6H4, para to SH),
6.50 (dd, 2 H, C6H4, para to NH), 6.42 (d, 2 H, C6H4, ortho to
NH), 4.80 (s, br., 2 H, NH), 3.27 (s, 8 H, C2H4), 2.70 (s, br., 2 H,
SH), 2.30 (s, 3 H, CH3, Ts). Ϫ 13C{1H} NMR (CDCl3): δ ϭ 147.6,
143.7, 135.5, 135.2, 129.8, 129.4, 127.1, 117.2, 111.6, 109.8 (C,
aryl), 48.8, 42.9 (C2H4), 21.4 (CH3, Ts).
h and then refluxed for 3 h. The yellow solid precipitating from the
green solution was separated, washed with THF (15 mL) and
MeOH (60 mL), and dried in vacuo. [Compound 7 was obtained
in equally high yields, when instead of 4 · EtOH the ligand
ЈTsN3H2S2Ј-H2 (3) was used]. Yield: 0.18
g
(32%).
Ϫ
C34H34N3PRuS2 (680.84): calcd. C 59.98, H 5.03, N 6.17, S 9.42;
found C 59.63, H 5.19, N 6.29, S 9.34. Ϫ IR (KBr): ν˜ ϭ 3288 w,
3258, 3247 m ν(NH) cmϪ1. Ϫ MS (FD, DMSO, 102Ru); m/z: 681
ЈN3H3S2Ј-H2 (4): Metallic sodium was added in small portions to
a solution of ЈTsN3H2S2Ј-H2 (3) (1.0 g, 2.1 mmol) in refluxing liquid
NH3 (100 mL) until the blue color of dissolved sodium persisted
for 10 min. Ammonium chloride was added until the blue color
disappeared, and the liquid NH3 was allowed to evaporate. The
resulting beige residue was dissolved in aqueous NaOH (0.4 g
NaOH in 100 mL H2O). The resulting H2O solution was extracted
with CH2Cl2 (70 mL) and filtered through filter pulp. Concentrated
hydrochloric acid was added to the H2O filtrate. When pH ϭ 8 was
reached, a white solid precipitated which was separated and washed
with H2O (40 mL). Recrystallization from EtOH yielded beige
needles of 4. The pH ϭ 8 proved critical, because further lowering
of the pH led to formation of yellow material, which had a gummy
consistency, proved insoluble in all common organic solvents, and
was not characterized in detail. Yield: 0.51 g (66%) of 4 · EtOH.
Ϫ C18H27N3OS2 (365.57): calcd. C 59.14, H 7.44, N 11.49, S 17.54;
found C 58.86, H 7.61, N 11.74, S 17.69. Ϫ IR (KBr): ν˜ ϭ 3376,
3317 m ν(NH), 2588 w, br. ν(SH) cmϪ1. Ϫ MS (FD, CH2Cl2); m/z:
319 [ЈN3H3S2Ј-H2]ϩ. Ϫ 1H NMR (CD2Cl2): δ ϭ 7.35 (d, 2 H,
C6H4), 7.15 (t, 2 H, C6H4), 6.68Ϫ6.53 (m, 4 H, C6H4), 3.50Ϫ3.10
(s, br., superimposed by t, 9 H, SH, NH, C2H4), 2.97 (t, 4 H, C2H4).
1
[Ru(PPh3)(ЈN3H3S2Ј)]ϩ. Ϫ H NMR ([D6]DMSO): δ ϭ 7.35Ϫ6.17
[m, 23 H, C6H4 and P(C6H5) superimposed], 5.77 (d, 2 H, NH),
4.41 (s, br., 1 H, NH), 3.75 (pseudo-t, 2 H, C2H4), 2.90 (pseudo-t,
2 H, C2H4), 2.75Ϫ2.20 (m, 4 H, C2H4). Ϫ 31P{1H} NMR
([D6]DMSO): δ ϭ 52.6 [s, P(C6H5)].
[Ru(PPh3)(ЈN3H3S2Ј-Me2)]I2 (8): Addition of MeI (0.50 mL, 8.0
mmol) to a yellow suspension of [Ru(PPh3)(ЈN3H3S2Ј)] (7) (0.13 g,
0.19 mmol) in THF (20 mL) yielded a beige suspension. The beige
solid was separated after 2 d, washed with THF (10 mL), and dried
in vacuo. Yield: 0.19 g (96%) 8 · THF. Ϫ C40H48I2N3OPRuS2
(1036.83): calcd. C 46.34, H 4.67, N 4.05, S 6.19; found C 46.18,
H 4.85, N 3.92, S 6.48. Ϫ IR (KBr): ν˜ ϭ 3284 w, br. ν(NH) cmϪ1
MS (FD, CH2Cl2, 102Ru); m/z: 838 {[Ru(PPh3)-
.
Ϫ
(ЈN3H3S2ЈϪMe2)](I)}ϩ, 711 [Ru(PPh3)(ЈN3H3S2Ј-Me2)]ϩ. Ϫ 1H
NMR ([D6]DMSO): δ ϭ 7.73Ϫ6.96 [m, 23 H, C6H4 and P(C6H5)
superimposed], 6.85 (d, 2 H, NH arom.), 6.46 (s, br., 1 H, NH
aliphat.), 4.06 (m, 2 H, C2H4), 2.92 (s, 6 H, SCH3), 2.87Ϫ2.72 (m,
6 H, C2H4). Ϫ 13C{1H} NMR ([D6]DMSO): δ ϭ 148.3 (C6H4),
133.2, 132.7 [d, P(C6H5)], 131.7, 131.2, 130.6 (C6H4), 129.8 [s, br.,
P(C6H5)], 128.2 (C6H4), 127.8 [d, P(C6H5)], 126.4 (C6H4), 60.0, 51.8
(C2H4), 25.3 (d, SCH3). Ϫ 31P{1H} NMR ([D6]DMSO): δ ϭ 37.5
[s, P(C6H5)].
Ϫ
13C{1H} NMR (CD2Cl2): δ ϭ 148.8, 135.1, 129.3, 117.3, 110.8,
110.8 (C6H4), 48.4, 43.6 (C2H4).
[Fe(ЈN3H3S2Ј)]2 (5): A yellow solution of ЈN3H3S2Ј-H2 · EtOH (4 ·
EtOH) (0.22 g, 0.60 mmol) and LiOMe (1.20 mmol, 1.20 mL of a
1  solution in MeOH) in THF (10 mL) was combined with a
solution of FeCl2 · 4 H2O (0.12 g, 0.60 mmol) in MeOH (10 mL).
A white solid precipitated which was separated, washed with
MeOH (15 mL), and dried in vacuo, in the course of which the
color of the solid changed from white to grey. Yield: 0.20 g (89%).
Ϫ C32H38Fe2N6S4 (746.66): calcd. C 51.48, H 5.13, N 11.26, S
17.18; found C 51.19, H 5.29, N 11.17, S 16.98. Ϫ IR (KBr): ν˜ ϭ
[Ru(PPh3)(ЈN3H2S2Ј-Me2)]I (11): [Ru(PPh3)(ЈN3H3S2Ј-Me2)]I2
·
THF (8 · THF) (0.10 g, 0.10 mmol) was suspended in N2H4 (1.0
mL). The yellow reaction mixture was stirred for 4 h and then
concentrated to dryness. The resulting yellow residue was dissolved
in CH2Cl2 (5 mL), insoluble material was removed by filtration,
and the filtrate was concentrated to dryness yielding a yellow pow-
der. Yield: 0.07 g (84%). Ϫ IR (KBr): ν˜ ϭ 3275 m ν(NH) cmϪ1. Ϫ
MS (FD, DMSO, 102Ru); m/z: 694 [Ru(PPh3)(ЈN3H2S2Ј-CH2)]ϩ. Ϫ
1H NMR (CD2Cl2): δ ϭ 7.57 [t, 2 H, CH(aryl)], 7.47Ϫ7.19 [m, 17
H, CH(aryl)], 6.97 [t, 1 H, CH(aryl)], 6.75 [d, 1 H, CH(aryl)], 6.31
[d, 1 H, CH(aryl)], 6.09 [t, 1 H, CH(aryl)], 5.72 (t, br., 1 H, NH),
5.46 (t, br., 1 H, NH), 3.46Ϫ2.60 (m, 8 H, C2H4), 2.36 (s, 3 H,
CH3), 1.75 (s, 3 H, CH3). Ϫ 13C{1H} NMR (CD2Cl2): δ ϭ 158.6,
147.3, 138.1 (d) (C6H4), 133.8, 133.6 [d, P(C6H5)], 131.9, 131.3,
131.0 (C6H4), 130.1 [s, br., P(C6H5)], 130.0, 129.6 (C6H4), 129.2 [d,
P(C6H5)], 127.2, 120.0, 111.4, 110.7 (C6H4), 58.7, 57.4, 55.8, 49.2
(C2H4), 28.2, 23.1 (d) (SCH3). Ϫ 31P{1H} NMR (CD2Cl2): δ ϭ
43.7 [s, P(C6H5)].
3145 m, br. ν(NH) cmϪ1
. Ϫ MS (FD, DMSO); m/z: 373
[Fe(ЈN3H3S2Ј)]ϩ. Ϫ µeff (293 K) ϭ 3.94 µB.
[Fe(CO)(ЈN3H3S2Ј)] (6): CO was continuously bubbled through a
solution of ЈN3H3S2Ј-H2 · EtOH (4 · EtOH) (0.135 g, 0.37 mmol)
and LiOMe (0.75 mmol, 0.75 mL of a 1  solution in MeOH) in
MeOH (15 mL). A solution of FeCl2 · 4 H2O (0.074 g, 0.37 mmol)
in MeOH (15 mL) was added and a red suspension formed. After
15 min, the resulting red solid was separated, washed with MeOH
(20 mL), and dried in vacuo. Yield: 0.15 g (97%) 6 · 0.5 MeOH. Ϫ
C17.5H21FeN3O1.5S2 (417.36): calcd. C 50.36, H 5.07, N 10.07, S
15.37; found C 50.35, H 4.88, N 10.27, S 15.59. Ϫ IR (KBr): ν˜ ϭ
3241, 3157, 3102 w ν(NH), 1930 s, 1910 vs ν(CO) cmϪ1. Ϫ IR
(THF): ν˜ ϭ 1934 vs ν(CO) cmϪ1. Ϫ MS (FD, DMSO); m/z: 373
[Fe(ЈN3H3S2Ј)]ϩ, 317 [(ЈN3H3S2Ј)]ϩ. Ϫ 1H NMR ([D6]DMSO): δ ϭ
7.26Ϫ6.50 (m, 9 H, C6H4 and NH superimposed), 5.86 (s, br., 1 H,
NH), 5.78 (s, br., 1 H, NH), 3.70Ϫ2.20 (m, 8 H, C2H4). Ϫ 13C{1H}
NMR ([D6]DMSO): δ ϭ 221.3 (CO), 153.6, 152.1, 151.1, 149.1,
129.0, 128.2, 124.7, 124.5, 122.4, 119.5, 119.4, 119.0 (C6H4), 62.2,
58.9, 46.2, 45.0 (C2H4).
[Ru(PPh3)(ЈN3H3S2Ј-Me2)](I)(Cl) (12) by Protonation of 11: Hydro-
chloric acid (0.50 mmol, 5 mL of a 0.1  solution of HCl in H2O)
was added to a yellow suspension of [Ru(PPh3)(ЈN3H2S2Ј-Me2)]I
(11) (0.04 g, 0.05 mmol) in MeOH (15 mL). The reaction mixture
was stirred for 5 min. Removal of the solvents yielded a yellow
powder (0.04 g).
Ϫ
MS (FD, CH2Cl2, 102Ru); m/z: 711
[Ru(PPh3)(ЈN3H3S2Ј-Me2)]ϩ, 695 [Ru(PPh3)(ЈN3H2S2Ј-Me)]ϩ, 681
[Ru(PPh3)(ЈN3H3S2Ј)]ϩ. Ϫ H NMR (CD2Cl2): δ ϭ 9.57 (t, br., 1
1
H, NH arom.), 9.37 (s, br., 1 H, NH arom.), 7.80Ϫ7.04 [m, 24 H,
C6H4, P(C6H5) and NH superimposed], 3.96Ϫ2.82 (m, 8 H, C2H4),
[Ru(PPh3)(ЈN3H3S2Ј)] (7): [RuCl2(PPh3)3] (0.79 g, 0.82 mmol) was 2.29 (s, 3 H, SCH3), 1.84 (s, 3 H, SCH3). Ϫ 13C{1H} NMR
added to a solution of ЈN3H3S2Ј-H2 · EtOH (4 · EtOH) (0.30 g,
0.82 mmol) and LiOMe (1.65 mmol, 1.65 mL of a 1  solution in
(CD2Cl2): δ ϭ 151.9, 151.4, 136.8, 134.3, 134.1 (d), 133.5 (d), 132.1,
131.9, 131.8, 131.2, 130.9, 129.6 (d), 129.2 (d), 128.8, 125.4, 125.1
346
Eur. J. Inorg. Chem. 1999, 341Ϫ348

Transition Metal Complexes with Sulfur Ligands, 135
FULL PAPER
129.1, 128.0, 127.6, 127.0, 125.2, 124.3, 123.8, 123.7, 123.6, 123.4,
122.5 (C6H4), 62.5, 58.5, 57.6, 57.1, 54.2, 52.0, 51.7, 51.4 (C2H4).
Table 2. Selected crystallographic data of [Ru(PPh3)(ЈN3H3S2Ј-
Me2)]I2 · 2 CH2Cl2 (8 · 2 CH2Cl2)
X-ray Structure Analysis of [Ru(PPh3)(ЈN3H3S2Ј-Me2)]I2 · 2 CH2Cl2
(8 · 2 CH2Cl2): Bright green columns of [Ru(PPh3)(ЈN3H3S2Ј-
Me2)]I2 · 2 CH2Cl2 (8 · 2 CH2Cl2) were grown from a saturated
CH2Cl2 solution of 8 which was layered with n-hexane. A suitable
single crystal was sealed under N2 in a glass capillary, and data
were collected with a Siemens P4 diffractometer. The structure was
solved by direct methods (SHELXTL-PLUS).[20] Full-matrix least-
squares refinement was carried out on F2 values (SHELXL-93).[21]
The hydrogen atoms were located in a difference Fourier synthesis
and isotropically refined. The hydrogen atoms of the CH2Cl2 solv-
ate molecules were calculated for ideal geometries. Their isotropic
temperature factors were fixed at 1.5 times the value for the C
atoms attached to them. For the atom Cl41, an obvious alternative
position exists, which, however, could not be refined. Table 2 con-
tains selected crystallographic data for [Ru(PPh3)(ЈN3H3S2Ј-Me2)]I2
· 2 CH2Cl2 (8 · 2 CH2Cl2).[22]
Compound
8·2 CH2Cl2
Formula
Mr [g/mol]
Crystal size [mm]
F(000)
C38H44Cl4I2N3PRuS2
1134.52
0.7 ϫ 0.5 ϫ 0.4
2232
P21/c
monoclinic
1602.7(4)
1738.8(4)
1695.5(4)
110.67(2)
4
4.421(2)
1.705
2.154
Space group
Cryst. system
a [pm]
b [pm]
c [pm]
β [°]
Z
V [nm3]
dcalcd. [g/cmϪ3
]
µ [mmϪ1
]
Diffractometer
Radiation [pm]
Temperature [K]
Scan technique
2θ range [°]
Siemens P4
Mo-Kα (λ ϭ 71.073)
163
ω scan
4.6Ϫ54.2
3.0Ϫ30.0
13956
Scan speed [°/min]
Meas. reflections
Indep. reflections
Obsd. reflections
σ criterion
Refined parameters
R1, wR2 (%)
Acknowledgments
9702
7037
F Ն 4σ(F)
620
Support of these investigations by the Deutsche Forschungsgemein-
schaft and Fonds der Chemischen Industrie is gratefully acknowl-
edged.
3.34, 9.18
[1] [1a]
D. P. Mellor in Chelating Agents and Metal Chelates (Eds.:
F. P. Dwyer, D. P. Mellor), Academic Press, New York, London,
1964, p. 44. Ϫ [1b] K. Burger, in Biocoordination Chemistry (Ed.:
K. Burger), Ellis Horwood, New York, 1990, p. 11.
(C, aryl), 59.1, 54.4, 53.6, 46.3 (NCH2), 28.4, 26.4 (d) (SCH3). Ϫ
31P{1H} NMR (CD2Cl2): δ ϭ 36.0 [s, P(C6H5)].
[2]
[2a] D. Sellmann, J. Sutter, Acc. Chem. Res. 1997, 30, 460Ϫ469.
[2b] D. Sellmann, W. Soglowek, F. Knoch, G. Ritter, J. Den-
[2c]
[Ru(NO)(ЈN3H2S2Ј)] (9): [RuCl3(NO)(PPh3)2] (0.42 g, 0.55 mmol)
was added to a solution of ЈN3H3S2Ј-H2 · EtOH (4 · EtOH) (0.20
g, 0.55 mmol) and LiOMe (1.64 mmol, 1.64 mL of a 1  solution
in MeOH) in THF (20 mL). The resulting black solution was
stirred for 48 h, during which time a green solid precipitated. The
solid was separated, washed with MeOH and THF (20 mL each),
and dried in vacuo. Yield: 0.14 g (57%). Ϫ C16H18N4ORuS2
(447.55): calcd. C 42.94, H 4.05, N 12.52, S 14.33; found C 42.96,
H 4.22, N 12.37, S 14.09. Ϫ IR (KBr): ν˜ ϭ 3245, 3224 m ν(NH),
1779 vs ν(NO) cmϪ1. Ϫ MS (FD, DMSO, 102Ru); m/z: 448
Ϫ
gler, Inorg. Chem. 1992, 31, 3711Ϫ3717. Ϫ
D. Sellmann,
W. Soglowek, F. Knoch, M. Moll, Angew. Chem. 1989, 101,
1244Ϫ1245; Angew. Chem. Int. Ed. Engl. 1989, 28, 1271Ϫ1272.
Ϫ
[2d] D. Sellmann, H. Kunstmann, F. Knoch, M. Moll, Inorg.
[2e]
Chem. 1988, 27, 4183Ϫ4190. Ϫ
D. Sellmann, T. Hofmann,
F. Knoch, Inorg. Chim. Acta 1994, 224, 61Ϫ71.
R. A. Henderson, G. J. Leigh, C. J. Picket, Adv. Inorg. Chem.
Radiochem. 1983, 27, 245.
[3]
[4]
[5]
D. Sellmann, J. Utz, F. W. Heinemann, Inorg. Chem., submitted.
Cf.: A. F. Childs, L. J. Goldsworthy, G. F. Harding, F. E. King,
A. W. Nineham, W. L. Norris, S. G. P. Plant, B. Selton, A. L.
L. Tompsett, J. Chem. Soc. 1948, 2174Ϫ2177.
Cf.: W. C. J. Ross, J. G. Wilson, J. Chem. Soc. 1959, 3616Ϫ3622.
Cf.: G. Klein, B. Prijs, Helv. Chim. Acta 1954, 37, 2057Ϫ2067.
D. Sellmann, R. Ruf, F. Knoch, M. Moll, Inorg. Chem. 1995,
34, 4745Ϫ4755.
1
[Ru(NO)(ЈN3H2S2Ј)]ϩ. Ϫ H NMR ([D6]DMSO): δ ϭ 7.83 (s, br.,
[6]
[7]
[8]
1 H, NH), 7.20 (d, 1 H, C6H4), 6.97Ϫ6.29 (m, 8 H, C6H4 and
NH superimposed), 3.89Ϫ2.77 (m, 8 H, C2H4). Ϫ 13C{1H} NMR
([D6]DMSO): δ ϭ 158.5, 146.6, 146.1, 137.9, 129.0, 127.0, 126.3,
125.0, 122.6, 121.7, 114.7, 108.3 (C6H4), 59.0, 57.7, 52.5, 50.5
(C2H4).
[9]
M. I. Bruce, F. G. A. Stone, J. Chem. Soc. A 1967, 1238Ϫ1241.
R. C. Roemmele, H. Rapoport, J. Org. Chem. 1988, 53,
2367Ϫ2371.
[10]
[11]
B. R. Cameron, D. A. House, A. McAuley, J. Chem. Soc., Dal-
ton Trans. 1993, 1019Ϫ1022.
[Ru(NO)(ЈN3H3S2Ј)]BF4 (10): Addition of HBF4 (0.30 mL of a 54%
solution in Et2O) to a green suspension of [Ru(NO)(ЈN3H2S2Ј)] (9)
(0.94 g, 2.12 mmol) in a 1:1 mixture (20 mL) of MeOH and Et2O
yielded a red suspension. The resulting red solid was separated after
3 h, washed with MeOH (5 mL), and dried in vacuo. Yield: 0.67 g
(59%). Ϫ C16H19BF4N4ORuS2 (535.36): calcd. C 35.90, H 3.58, N
10.47, S 11.98; found C 36.12, H 3.56, N 10.42, S 11.69. Ϫ IR
(KBr): ν˜ ϭ 3293, 3238, 3219 w ν(NH), 1855 vs ν(NO), 1084 s
[12] [12a]
D. Sellmann, H. Kunstmann, F. Knoch, M. Moll, Inorg.
Chem. 1988, 27, 4183Ϫ4190. Ϫ [12b] D. Sellmann, C. Rohm, M.
Moll, F. Knoch, Z. Naturforsch. 1995, 50b, 1229Ϫ1244.
[13] [13a]
D. Sellmann, R. Ruf, F. Knoch, M. Moll, Inorg. Chem.
[13b]
1995, 34, 5963Ϫ5972. Ϫ
D. Sellmann, O. Käppler, F.
Knoch, M. Moll, Z. Naturforsch. 1990, 45b, 803Ϫ816.
M. L. Tobe, Adv. Inorg. Bioinorg. Mech. 1983, 2, 1.
J. J. Levison, S. D. Robinson, J. Chem. Soc. A 1970, 2947Ϫ2954.
T. A. Stephenson, G. Wilkinson, J. Inorg. Nucl. Chem. 1966,
28, 945Ϫ956.
L. Qian, Z. Sun, M. P. Mertes, K. Bowman Mertes, J. Org.
Chem. 1991, 56, 4904Ϫ4907.
R. F. Hunter, J. Chem. Soc. 1930, 125Ϫ147.
F. P. Schmidtchen, Chem. Ber. 1980, 113, 2175Ϫ2182.
SHELXTL-PLUS for Siemens Crystallographic Research Sys-
tems, Release 4 21/V, Siemens Analytical X-ray Instruments
Inc., Madison, WI, 1990.
[14]
[15]
[16]
ν(BF4) cmϪ1
.
Ϫ
MS (FD, DMSO, 102Ru); m/z: 448
[Ru(NO)(ЈN3H2S2Ј)]ϩ. Ϫ 1H NMR ([D6]DMSO): δ ϭ 10.04 (m,
0.6 H, NH arom.), 8.42 (m, 0.3 H, NH arom.), 8.24 (s, br., 0.3 H,
NH arom.), 8.05 (s, br., 0.6 H, NH arom.), 7.67Ϫ6.87 (m, 8 H,
C6H4), 4.41 (m, 0.3 H, NH aliphat.), 4.10 (m, 0.6 H, NH aliphat.),
3.94Ϫ2.95 (m, 8 H, C2H4). Ϫ 13C{1H} NMR ([D6]DMSO): δ ϭ
150.9, 148.5, 147.4, 147.3, 145.0, 143.1, 142.2, 141.3, 129.7, 129.2,
[17]
[18]
[19]
[20]
Eur. J. Inorg. Chem. 1999, 341Ϫ348
347

D. Sellmann, J. Utz, F. W. Heinemann
FULL PAPER
[21]
G. M. Sheldrick, SHELXL-93, Program for crystal structure re-
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].
Received August 7, 1998
finement, Universität Göttingen, 1993.
Crystallographic data (excluding structure factors) for the struc-
[22]
ture of [Ru(PPh3)(ЈN3H3S2Ј-Me2)]I2 · 2 CH2Cl2 have been de-
posited with the Cambridge Crystallographic Data Centre as
supplementary publication no. CCDC-100956. Copies of the
[I98278]
348
Eur. J. Inorg. Chem. 1999, 341Ϫ348