Transition metal complexes with sulfur ligands, 139. - Synthesis and exchange reactions of sulfur-rich nickel and palladium [M(L)('S3')] complexes ['S3'2- = bis(2-mercaptophenyl)sulfide(2-)]

Article abstract of DOI:10.1002/(sici)1099-0682(200002)2000:2<271::aid-ejic271>3.0.co;2-m

In order to obtain suitable precursors for nickel and palladium complexes that model the reactivity of the active sites of hydrogenases and CO dehydrogenases, a series of [M(L)('S₃')] complexes has been synthesized [M = Ni(II), Pd(II), 'S₃'^2- = bis(2-mercaptophenyl)sulfide(2-)]. X-ray structure determinations of [Ni('S₃')]₃ (1) and [Pd('S₃')]₃ (2) have revealed that the [M('S₃')] fragments trimerize to give six-membered [MS]₃ rings, which exhibit chair conformations with alternating M(II) centers and thiolate bridging atoms. Reactions of the parent complex [Ni('S₃')]₃ (1) with nucleophiles L, such as thiolates SR^- (R = tBu, Cy, Me, Ph), phosphanes PR₃ (R = Cy, Ph), chloride, or azide, have been found to yield the corresponding anionic or neutral [Ni(L)('S₃')] complexes, which were isolated as (NBu₄)[Ni(SR)('S₃')] [R = tBu (3), Cy (4), Me (5), Ph (6)], [Ni(PR₃)('S₃')] [R = Cy (7), Ph (8)], (NBu₄)[Ni(Cl)('S₃')] (9), and (NBu₄)[Ni(N₃)('S₃')] (10). When treated with Me₃SiX, the StBu^- ligand in (NBu₄)[Ni(StBu)('S₃')] (3) was exchanged to give (NBu₄)[Ni(X)('S₃')] [X = Cl^- (9), N₃^- (10), NCS- (11), NSO^- (12)]. The palladium complex [Pd('S₃')]₃ (2) could also be cleaved with StBu^-, but the resulting (NBu₄)[Pd(StBu)('S₃')] (13) proved inert towards exchange reactions with Me₃SiX. All the mononuclear complexes have been characterized by standard spectroscopic techniques and by elemental analysis. The molecular structures of 3, 4, 6, 7, 8, 9, and 13 have been determined by X-ray crystallography. The [MS₃L] core geometries of all the complexes are non-planar, exhibiting a considerable tetrahedral distortion.

Full text of DOI:10.1002/(sici)1099-0682(200002)2000:2<271::aid-ejic271>3.0.co;2-m

FULL PAPER
Transition Metal Complexes with Sulfur Ligands, 139[°]
Synthesis and Exchange Reactions of Sulfur-Rich Nickel and Palladium
[M(L)(‘S3’)] Complexes [‘S3’2– ؍ Bis(2-mercaptophenyl)sulfide(2–)]
Dieter Sellmann,*[a] Franz Geipel,[a] and Frank W. Heinemann[a]
Dedicated to Professor Egon Uhlig on the occasion of his 70th birthday
Keywords: Nickel complexes / Palladium complexes / S ligands / Exchange reactions / Azide / Sulfinylimide
In order to obtain suitable precursors for nickel and
palladium complexes that model the reactivity of the active
[Ni(PR3)(‘S3’)] [R = Cy (7), Ph (8)], (NBu4)[Ni(Cl)(‘S3’)] (9), and
(NBu4)[Ni(N3)(‘S3’)] (10). When treated with Me3SiX, the
sites of hydrogenases and CO dehydrogenases, a series of StBu– ligand in (NBu4)[Ni(StBu)(‘S3’)] (3) was exchanged to
–
[M(L)(‘S3’)] complexes has been synthesized [M = NiII, PdII;
‘S3’2– = bis(2-mercaptophenyl)sulfide(2–)]. X-ray structure
determinations of [Ni(‘S3’)]3 (1) and [Pd(‘S3’)]3 (2) have
revealed that the [M(‘S3’)] fragments trimerize to give six-
membered [MS]3 rings, which exhibit chair conformations
with alternating MII centers and thiolate bridging atoms.
Reactions of the parent complex [Ni(‘S3’)]3 (1) with
nucleophiles L, such as thiolates SR– (R = tBu, Cy, Me, Ph),
phosphanes PR3 (R = Cy, Ph), chloride, or azide, have been
found to yield the corresponding anionic or neutral
give (NBu4)[Ni(X)(‘S3’)] [X = Cl– (9), N3 (10), NCS– (11),
NSO– (12)]. The palladium complex [Pd(‘S3’)]3 (2) could also
be
cleaved
with
StBu–,
but
the
resulting
(NBu4)[Pd(StBu)(‘S3’)] (13) proved inert towards exchange
reactions with Me3SiX. All the mononuclear complexes have
been characterized by standard spectroscopic techniques
and by elemental analysis. The molecular structures of 3, 4,
6, 7, 8, 9, and 13 have been determined by X-ray
crystallography. The [MS3L] core geometries of all the
complexes are non-planar, exhibiting
tetrahedral distortion.
a
considerable
[Ni(L)(‘S3’)]
complexes,
which
were
isolated
as
(NBu4)[Ni(SR)(‘S3’)] [R = tBu (3), Cy (4), Me (5), Ph (6)],
Introduction
Much of the current interest in nickel thiolateϪthioether
complexes stems from the discovery that nickel in sulfur-
rich coordination spheres forms the active centers of en-
zymes such as hydrogenases[1] and CO dehydrogenases.[2]
In the quest for model compounds of these enzymes, a con-
siderable number of new nickel complexes with different do-
nor sets and geometries has been synthesized.[3,4,5] How-
ever, complexes exhibiting structural (NiϪS coordination)
and functional (catalysis of enzyme reactions) features of
the enzymes have remained extremely rare. Our search for
such compounds has recently yielded complexes containing
[M(‘S3’)] fragments (M ϭ Ni, Pt) with the tridentate ligand
‘S3’2Ϫ ϭ bis(2-mercaptophenyl)sulfide(2Ϫ).[6]
genases, dihydrogen and hydride are, of course, the sub-
strates of primary interest. Unfortunately, however, all at-
tempts to coordinate these species to [Ni(‘S3’)] fragments
have to date been unsuccessful,[6] despite the fact that NMR
spectroscopic investigations have yielded conclusive evi-
dence for the formation of [Pt(H)(‘S3’)]Ϫ.[6] Further experi-
ments showed that a favored reaction of [M(‘S3’)] fragments
is oligomerization to give either dinuclear [Ni(‘S3’)]2 or tri-
nuclear [Pt(‘S3’)]3. These complexes contain thiolate
bridges, which block the fourth coordination site at the me-
tal centers. As a consequence, they are extremely sparingly
soluble in all common solvents such that homogeneous
phase reactions are prevented. The thiolate bridges in
[Ni(‘S3’)]2 or [Pt(‘S3’)]3 may be cleaved by nucleophiles such
as PMe3 or cyanide. The resulting mononuclear [M(L)(‘S3’)]
derivatives are much more soluble than the parent com-
plexes, but the coligands L proved to be inert.[6] Thus, the
aim of the work described herein was to obtain [M(L)(‘S3’)]
species with exchangeable coligands L and thus a readily
accessible coordination site.
The [M(‘S3’)] fragments with d8 electron metal(II) centers
were anticipated to have an accessible site for the coordi-
nation and activation of substrates. With regard to hydro-
[°]
Part 138: D. Sellmann, D. Häußinger, F. W. Heinemann, Eur.
J. Inorg. Chem. 1999, 1715Ϫ1725.
[a]
Institut für Anorganische Chemie der Universität Erlangen-
Nürnberg,
Egerlandstraße 1, D-91058 Erlangen, Germany
Fax: (internat.) ϩ 49-(0)9131/852-7367
E-mail: sellmann@anorganik.chemie.uni-erlangen.de
Eur. J. Inorg. Chem. 2000, 271Ϫ279
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
1434Ϫ1948/00/0202Ϫ271 $ 17.50ϩ.50/0
271

D. Sellmann, F. Geipel, F. W. Heinemann
FULL PAPER
dark-brown to black salts (NBu4)[Ni(SR)(‘S3’)] with R ϭ
tBu (3), Cy (4), Me (5), and Ph (6). These salts were found
to be readily soluble in THF, acetone, MeOH, and CH2Cl2,
but insoluble in Et2O and n-hexane. The molecular struc-
tures of (NBu4)[Ni(StBu)(‘S3’)] (3), (NBu4)[Ni(SCy)(‘S3’)]
(4), and (NBu4)[Ni(SPh)(‘S3’)] (6) were determined by X-
ray diffraction analysis.
Results
Cleavage of [Ni(‘S3’)]3 and Substitution Reactions of
[Ni(L)(‘S3’)] Complexes (L ؍ PR3, SR؊)
The extremely insoluble [Ni(‘S3’)]2 parent complex has
previously been obtained from Ni(ac)2 · 4 H2O and ‘S3’-
H2.[6] A solvothermal recrystallization from hot DMF
(175°C) in a sealed ampoule yielded single crystals, X-ray
structure analysis of which showed the product to contain
dinuclear [Ni(‘S3’)]2. On repeating the synthesis, we have
now obtained single crystals from the mother liquor of the
reaction solution at room temperature. An X-ray structure
determination of these crystals revealed that they consisted
of the trinuclear [Ni(‘S3’)]3 (1). Complex 1 is structurally
analogous to [Pt(‘S3’)]3 and shows that the crystallization
conditions can influence the trimerization vs. dimerization
of [Ni(‘S3’)] fragments. These results prompted us to synthe-
size [Pd(‘S3’)]3 (2) as well (for the sake of completeness).
Complex 2 was obtained from ‘S3’-Li2 and [PdCl2(COD)]
(Scheme 1).
Reactions with the bulky phosphanes PCy3 and PPh3
were then investigated in order to probe the lability of the
phosphanes and the potential for formation of agostic
CϪH···Ni interactions in [Ni(PR3)(‘S3’)] complexes. The
[Ni(PR3)(‘S3’)] complexes with R ϭ Cy (7), Ph (8) were re-
adily formed from THF suspensions of [Ni(‘S3’)]3 and the
respective phosphanes. They were fully characterized but
proved as inert to substitution as [Ni(PMe3)(‘S3’)]. No agos-
tic CϪH···Ni interactions could be detected, neither by X-
1
ray structure determinations nor by H-NMR spectra.
Halides and Pseudohalides as Nucleophiles
Initial attempts to cleave [Ni(‘S3’)]3 with weak nucleo-
philes such as chloride from NMe4Cl to give the
[Ni(Cl)(‘S3’)]Ϫ anion invariably proved unsuccessful. How-
ever, this anion was readily formed when the StBu deriva-
tive (NBu4)[Ni(StBu)(‘S3’)] (3) was treated with Me3SiCl.
The resulting (NBu4)[Ni(Cl)(‘S3’)] (9) has been fully charac-
terized and its molecular structure has been determined by
X-ray diffraction analysis.
Since these results proved the viability of [Ni(Cl)(‘S3’)]Ϫ,
we repeated the attempts to cleave [Ni(‘S3’)]3 directly with
chloride, but employed NBu4Cl instead of NMe4Cl. Indeed,
when suspensions of [Ni(‘S3’)]3 in THF were treated with
equimolar amounts of NBu4Cl at room temperature, (NBu4)-
[Ni(Cl)(‘S3’)] (9) was formed in yields in excess of 70%.
Analogously, (NBu4)[Ni(N3)(‘S3’)] (10) was obtained first
from (NBu4)[Ni(StBu)(‘S3’)] (3) and Me3SiN3 and sub-
sequently from the direct reaction between [Ni(‘S3’)]3 and
NBu4N3. Syntheses of (NBu4)[Ni(NCS)(‘S3’)] (11) and
(NBu4)[Ni(NSO)(‘S3’)] (12) required the “silylating” pro-
cedure. Thus, complexes 11 and 12 were obtained from
(NBu4)[Ni(StBu)(‘S3’)] (3) using Me3SiNCS and Me3Si-
NSO, respectively. The driving force behind these syntheses
is presumably the formation of Me3SiStBu. Attempts to ob-
tain (NBu4)[Ni(NCO)(‘S3’)] using either of the aforemen-
tioned two methods proved unsuccessful.
The palladium complex [Pd(‘S3’)]3 (2) could also be
cleaved with StBuϪ to yield (NBu4)[Pd(StBu)(‘S3’)] (13).
Exploratory experiments showed the StBuϪ ligand in 13 to
be inert. For example, treatment of 13 with Me3SiX (X ϭ
Cl, N3, NCS, or NSO) did not yield the corresponding
[Pd(X)(‘S3’)]Ϫ ions.
Scheme 1. Synthesis and reactions of [Ni(‘S3’)] and [Pd(‘S3’)] com-
plexes
In order to achieve an all-sulfur coordination of the
nickel center, we first examined reactions of [Ni(‘S3’)]3 with
thiolates. Both small and sterically demanding thiolates,
such as SMeϪ and SCyϪ, gave essentially the same results.
When black-brown THF suspensions of [Ni(‘S3’)]3 (1) were
treated with MeOH solutions of the respective NaSR salts
at room temperature, dark-brown solutions resulted. Ad-
Characterization of Complexes and Monitoring of
Reactions
All the complexes are diamagnetic and have been charac-
dition of NBu4OH and subsequent workup yielded the terized by standard spectroscopic techniques and elemental
272
Eur. J. Inorg. Chem. 2000, 271Ϫ279

Transition Metal Complexes with Sulfur Ligands, 139
FULL PAPER
analysis. Several of the complexes have also been charac-
terized by X-ray structure analysis. In contrast to the ex-
tremely insoluble starting complexes [M(‘S3’)]3, all
[M(L)(‘S3’)] derivatives with phosphane or anionic col-
igands L proved sufficiently soluble in THF, acetone, or
CH2Cl2 to allow recording of their NMR spectra. The solu-
tions are black-brown (3Ϫ6), orange (12), red (7, 8, 11, 13),
or violet (9, 10).
1
The H-NMR splitting pattern of the aromatic protons
is a typical feature of the [M(‘S3’)] fragment and can be
used as a “fingerprint” of the individual complexes since
Figure 2. (a) IR spectrum of the reaction solution containing
(NBu4)[Ni(StBu)(‘S3’)], Me3SiN3, and the resulting (NBu4)-
[Ni(N3)(‘S3’)], (b) UV/Vis monitoring of the reaction between
(NBu4)[Ni(StBu)(‘S3’)] and Me3SiN3 in THF
X-ray Structure Determinations
Several of the complexes were obtained in the form of
single crystals suitable for X-ray structure analysis. Figure
3 depicts the mononuclear structures, showing different
views of the individual species. Table 1 lists selected dis-
tances and angles.
1
Figure 1. Aromatic region of the H-NMR spectra of (a) (NBu4)-
All the complexes were found to consist of discrete mol-
ecules or ions. The [M(‘S3’)] fragments invariably exhibit the
characteristic butterfly-shape, which arises from the rigid
‘S3’ topology and sp3 hybridization of the central S(thic-
ether) donor.[6] The ‘S3’ topology is also responsible for the
tetrahedral distortion of the [MS3L] cores, which are not
planar as might have been expected for low-spin four-coor-
[Ni(StBu)(‘S3’)] in [D8]THF, (b) 2 h after addition of Me3SiN3, and
(c) after 12 h and almost complete formation of (NBu4)-
[Ni(N3)(‘S3’)]
the multiplet shifts specifically depend on the coligands L.
Figure 1 illustrates the H-NMR spectroscopic monitor- dinate d8 electron metal(II) centers. Figure 4 illustrates this
1
ing of the reaction between (NBu4)[Ni(StBu)(‘S3’)] (3) and tetrahedral distortion in [Ni(Cl)(‘S3’)]Ϫ.
Me3SiN3. The clean aromatic multiplets demonstrate that
Distances and angles show no anomalies. It has been
complex 3 is converted into the azido complex 10 without pointed out previously that the MϪS(thiother) distances
the formation of any other complexes as by-products. This are invariably shorter than the corresponding MϪS(thiol-
is further corroborated by the IR spectrum and, in particu- ate) distances and are practically unaffected by the trans
lar, the UV/Vis spectrum of the reaction solution, which ligands L. Because the ligands used here range from “hard”
shows two isosbestic points (Figure 2). In all cases, the chloride, through “soft” σ-π donating thiolates, to σ-donor/
13C{1H}-NMR spectra of the mononuclear complexes exhi- π-acceptors such as phosphanes, the [M(‘S3’)] fragments
bit six 13C signals for the twelve aromatic C atoms of the evidently also exhibit the structural invariance that has pre-
‘S3’ ligand, in accordance with the twofold symmetry of the viously been noted as a typical feature of [MSx] centers.[7]
[M(‘S3’)] fragments. Strong and characteristic bands in the The molecular structure of the PCy3 complex [Ni(P-
IR spectra are well suited for identifying the complexes 10 Cy3)(‘S3’)] (7) differs from those of all the other complexes
(2037 cmϪ1), 11 (2105 cmϪ1), and 12 (1230, 1030 cmϪ1).
in that it has crystallographic CS symmetry.
Eur. J. Inorg. Chem. 2000, 271Ϫ279
273

D. Sellmann, F. Geipel, F. W. Heinemann
FULL PAPER
Figure 3. ORTEP plots of (a) (NBu4)[Ni(StBu)(‘S3’)] (3), (b) (NBu4)[Ni(Cl)(‘S3’)] (9), (c) (NBu4)[Pd(StBu)(‘S3’)] (13), (d) (NBu4)[Ni(S-
Cy)(‘S3’)] (4), (e) (NBu4)[Ni(SPh)(‘S3’)] (6), (f) [Ni(PPh3)(‘S3’)] · CDCl3 (8 · CDCl3), and (g) [Ni(PCy3)(‘S3’)] · THF (7 · THF); 50% proba-
bility ellipsoids; hydrogen atoms, solvent molecules and counterions omitted for the sake of clarity; different projections were chosen to
illustrate the tetrahedral distortion of the [M(‘S3’)] fragments
Table 1. Selected distances [pm] and angles [°] in (NBu4)[Ni(StBu)(‘S3’)] (3), (NBu4)[Ni(SCy)(‘S3’)] (4), (NBu4)[Ni(SPh)(‘S3’)] (6),
[Ni(PCy3)(‘S3’)] · THF (7 · THF), [Ni(PPh3)(‘S3’)] · CDCl3 (8 · CDCl3), (NBu4)[Ni(Cl)(‘S3’)] (9), and (NBu4)[Pd(StBu)(‘S3’)] (13)
Compound
[Ni]ϪStBu (3) [Ni]ϪSCy (4)
[Ni]ϪSPh (6)
[Ni]ϪPCy3 (7) [Ni]ϪPPh3 (8) [Ni]ϪCl (9)
[Pd]ϪStBu (13)
M1ϪS1
M1ϪS2
M1ϪS3
M1ϪL
S1ϪM1ϪS2 90.86(6)
S1ϪM1ϪS3 160.88(7)
S2ϪM1ϪS3 86.66(6)
S1ϪM1ϪL
S2ϪM1ϪL
S3ϪM1ϪL
217.2(2)
214.2(1)
221.2(2)
219.2(2)
218.3(2)
211.9(2)
216.8(2)
219.2(2)
89.47(6)
160.09(6)
89.73(6)
97.40(7)
163.70(6)
88.75(6)
217.5(1)
211.5(1)
218.0(1)
220.0(1)
90.00(5)
159.78(5)
89.46(5)
96.89(6)
164.95(5)
88.64(5)
217.6(1)
217.5(1)
213.1(1)
215.8(1)
219.7(1)
89.14(3)
159.73(4)
89.85(3)
91.64(3)
164.11(3)
94.81(3)
217.0(1)
211.4(2)
219.5(2)
220.6(2)
91.05(7)
161.31(6)
87.86(7)
92.32(7)
166.90(6)
92.93(7)
229.1(1)
226.0(2)
231.0(1)
233.3(2)
88.44(5)
164.04(6)
86.96(5)
95.72(6)
175.72(5)
89.30(6)
213.3(1)
217.6(1)[a]
220.9(1)
88.72(3)
163.66(5)[a]
88.72(3)[a]
94.01(3)
100.68(6)
164.04(7)
85.91(6)
159.55(5)
94.01(3)[a]
[a]
1
S3 ϭ S1a (symmetry code: x, Ϫy Ϫ /2, z).
[Pd(‘S3’)]3 (2) exhibit a cyclohexane-like [MIIS]3 six-mem-
bered ring with a chair conformation that leads to a charac-
teristic propeller-like twist of the three [M(‘S3’)] units (Fig-
ure 5b). Related structures have been found for [Ni(‘µ-
S2C3Me2’)]3,[5e] [Ni(‘tBuS4’)]3,[8] and [Pd(SC2H4SC2H4S)]3.[9]
Figure 4. View showing the tetrahedral [NiClS3] core distortion
in [Ni(Cl)(‘S3’)]Ϫ
Concluding Discussion
Figure 5 depicts views of the two trinuclear [M(‘S3’)]3
The trinuclear complex [Ni(‘S3’)]3 (1) has been charac-
complexes 1 and 2 from different angles, while Table 2 lists terized. Complex 1 and the similarly new [Pd(‘S3’)]3 (2) now
selected distances and angles. Like the previously described complete the series of [M(‘S3’)]3 complexes with NiII, PdII,
[Pt(‘S3’)]3 complex,[6] the trinuclear [Ni(‘S3’)]3 (1) and and PtII. The extremely sparingly soluble [Ni(‘S3’)]3 (1) gave
274
Eur. J. Inorg. Chem. 2000, 271Ϫ279

Transition Metal Complexes with Sulfur Ligands, 139
FULL PAPER
Figure 5. (a) Molecular structures of the [M(‘S3’)]3 complexes (1·3 THF·6 MeOH) (M ϭ Ni), and (2·2 CH2Cl2) (M ϭ Pd); 50% probability
ellipsoids; hydrogen atoms and solvent molecules omitted for the sake of clarity; (b) view showing the chair conformation of the [MS]3
rings
Table 2. Selected distances [pm] and angles [°] in [Ni(L)(‘S3’)] complexes that had previously been found to
[Ni(‘S3’)]3 · 3 THF · 6 MeOH
(1 · 3 THF · 6 MeOH),
and
be inaccessible by direct reaction of [Ni(‘S3’)]3 and the re-
spective L. It is noteworthy that (NBu4)[Ni(N3)(‘S3’)] (10)
represents one of the few azido complexes in which a hard
azide ligand is bound to a sulfur-rich metal complex frag-
ment.[10] Very few such NSO complexes have been re-
ported[11] and, to the best of our knowledge, (NBu4)[Ni(N-
SO)(‘S3’)] (12) represents the first NSO complex with an
[MSx] center.
[Pd(‘S3’)]3 · 2 CH2Cl2 (2 · 2 CH2Cl2)
[c]
Compound
[Ni(‘S3’)]3 (1)
[Pd(‘S3’)]3 (2)
M1ϪS1
M1ϪS2
M1ϪS3
M1ϪL
M1···M2
S3···L
214.2(2)
213.4(2)
221.4(2)
229.0(7)
226.3(7)[d] 226.6(7)[e]
226.6(7)
236.1(7)
225.7(7)
232.6(7)
226.4(7)
234.3(7)
218.4(2)[a] 233.8(7)[f]
333.6(2)[b] 337.9(4)
311.0(4)[a] 337.8(9)[f]
229.7(7)[g] 229.8(7)[h]
355.3(4)[i]
340.9(4)[j]
325.6(9)[h] 333.3(9)[k]
S1ϪM1ϪS2 90.7(1)
S1ϪM1ϪS3 163.5(1)
S2ϪM1ϪS3 87.7(1)
88.2(3)
166.7(2)
86.1(2)
95.2(3)[f]
89.2(3)
87.5(3)
164.8(3)
86.7(2)
166.2(3)
87.4(2)
Experimental Section
S1ϪM1ϪL
S2ϪM1ϪL
S3ϪM1ϪL
94.4(1)[a]
96.4(3)[g]
94.7(3)[h]
General Methods: Unless noted otherwise, all reactions and oper-
ations were carried out under nitrogen using standard Schlenk
techniques. Solvents were dried and distilled prior to use. Ϫ As
far as possible, reactions were monitored by IR or NMR spec-
troscopy. Spectra were recorded on the following instruments: IR
(KBr discs or CaF2 cuvettes, solvent bands were compensated):
PerkinϪElmer 983, 1620 FT-IR, and 16PC FT-IR. Ϫ NMR: Jeol
JNM-GX 270, EX 270, and Lambda LA 400 with the residual
protio-solvent signal used as an internal reference. Chemical shifts
are quoted on the δ scale (downfield shifts are positive) relative
to tetramethylsilane (1H, 13C{1H} NMR) or 85% H3PO4 (31P{1H}
NMR); spectra were recorded at 25°C. Ϫ UV/Vis: Shimadzu
169.6(1)[a] 172.6(2)[f]
170.8(3)[g] 172.9(3)[h]
90.0(1)[a]
91.9(3)[f]
93.0(3)
89.6(2)[g]
100.4(3)[l]
91.9(2)[h]
93.5(2)[m]
M1ϪS3ϪM2 98.7(1)[b]
[a]
[b]
L ϭ S3a (symmetry code: Ϫy Ϫ 1, x Ϫ y Ϫ 1, z). Ϫ
M2 ϭ
Ni1b (symmetry code: Ϫx ϩ y, Ϫx Ϫ 1, z). Ϫ [c] Three independent
[d]
[e]
[f]
[g]
[Pd(‘S3’)] units. Ϫ
Pd2ϪS4. Ϫ
Pd3ϪS7. Ϫ L ϭ S9. Ϫ
L ϭ S3. Ϫ [h] L ϭ S6. Ϫ [i] Pd2ϪPd3. Ϫ [j] Pd3ϪPd1. Ϫ [k] S6ϪS9.
[l]
[m]
Ϫ
Pd2ϪS6ϪPd3. Ϫ
Pd3ϪS9ϪPd1.
mononuclear [Ni(L)(‘S3’)] complexes with L ϭ thiolates,
phosphanes, halides, and pseudohalides, which proved to be
much more soluble than 1. The chloro ligand in (NBu4)[Ni-
(Cl)(‘S3’)] (9) and the StBuϪ ligand in (NBu4)[Ni-
(StBu)(‘S3’)] (3) were found to be labile, making 3 and 9
UV3101 PC spectrophotometer.
Ϫ
Mass spectra: Jeol
MSTATION 700 spectrometer. Ϫ Elemental analyses: Carlo Erba
EA 1106 or 1108 analyzer. Ϫ Me3SiCl, Me3SiN3, Me3SiNCS,
suitable starting materials for the synthesis of other NBu4Cl, and PR3 were purchased from either Aldrich or Fluka;
Eur. J. Inorg. Chem. 2000, 271Ϫ279 275

D. Sellmann, F. Geipel, F. W. Heinemann
‘S3’-H2,[6] [PdCl2(COD)],[12] and Me3SiNSO[13] were prepared ac- (1.20 mmol) of a 0.8  solution of NBu4OH in MeOH; 20 mL of
FULL PAPER
cording to literature methods.
THF. Yield: 494 mg (69%). Ϫ C29H47NNiS4 (596.63): calcd. C
58.38, H 7.94, N 2.35, S 21.49; found C 58.11, H 8.27, N 2.39, S
21.39. Ϫ 1H NMR (269.6 MHz, [D6]acetone): δ ϭ 7.66 (d, 2 H,
C6H4), 7.21 (d, 2 H, C6H4), 6.96 (m, 2 H, C6H4), 6.84 (m, 2 H,
C6H4), 3.50 (t, 8 H, NCH2), 1.78 (m, 8 H, NCH2CH2), 1.59 (s, 3 H,
SCH3), 1.38 [m, 8 H, N(CH2)2CH2], 0.90 [t, 12 H, N(CH2)3CH3]. Ϫ
13C{1H} NMR (67.7 MHz, [D6]acetone): δ ϭ 156.9, 134.9, 129.8,
128.4, 128.2, 121.2 (C6H4), 59.5, 24.6, 20.4, 13.9, 11.1 (SCH3,
NC16H36).
[Ni(‘S3’)]3 (1): A solution of ‘S3’ϪH2 (4.327 g, 17.28 mmol) in THF
(70 mL) was added dropwise to Ni(ac)2 · 4 H2O (4.300 g,
17.28 mmol) in MeOH (10 mL) and the resulting brown suspension
was refluxed for 4 h. The black-brown precipitate was then sepa-
rated by filtration, washed with THF (50 mL), and dried in vacuo.
A second batch of the product was obtained in the form of single
crystals on slow evaporation of the solvent from the filtrate at room
temperature. Yield: 5.093 g of 1·THF (89%). Ϫ C40H32Ni3OS9
(993.41): calcd. C 48.36, H 3.25, S 29.05; found C 48.01, H 3.03,
S 30.58.
(NBu4)[Ni(SPh)(‘S3’)] (6): 845 mg (0.92 mmol) of 1; 5.52 mL
(2.76 mmol) of a 0.5  solution of NaSPh in MeOH; 3.50 mL
(2.80 mmol) of a 0.8  solution of NBu4OH in MeOH; 20 mL of
THF. Yield: 1.400 g (77%). Ϫ C34H49NNiS4 (658.70): calcd. C
61.99, H 7.50, N 2.13, S 19.47; found C 62.03, H 7.47, N 2.14, S
19.57. Ϫ 1H NMR (269.6 MHz, CD2Cl2): δ ϭ 7.70 (d, 2 H, C6H5),
7.55 (d, 2 H, C6H4), 7.21 (d, 2 H, C6H4), 7.02Ϫ6.84 (m, 7 H, C6H5,
C6H4), 3.18 (t, 8 H, NCH2), 1.50 (m, 8 H, NCH2CH2), 1.29 [m, 8
H, N(CH2)2CH2], 0.87 [t, 12 H, N(CH2)3CH3]. Ϫ 13C{1H} NMR
(67.7 MHz, CD2Cl2): δ ϭ 155.0, 140.3, 133.8, 134.4, 129.4, 128.1,
127.7, 127.2, 122.6, 121.4 (C6H5, C6H4), 59.4, 24.6, 20.3, 13.9
(NC16H36).
[Pd(‘S3’)]3 (2): A solution of ‘S3’ϪH2 (1.327 g, 5.3 mmol) in THF
(30 mL) was combined with nBuLi (4.24 mL, 10.6 mmol) at Ϫ50°C
and the mixture was subsequently allowed to warm to room tem-
perature. Addition of [PdCl2(COD)] led to a dark-red reaction mix-
ture, which was stirred at room temperature overnight and then
stored at Ϫ30°C for 24 h. A brown solid precipitated, which was
separated, washed with MeOH/THF, and dried in vacuo. Yield:
1.536 g of 2 · THF (77%). Ϫ C40H32OPd3S9 (1136.48): calcd. C
42.28, H 2.84, S 25.39; found C 42.29, H 2.71, S 24.79.
(NBu4)[Ni(SR)(‘S3’)], where R ؍ tBu (3), Cy (4), Me (5), Ph (6) ؊
General Procedure: The appropriate thiol was first deprotonated in
MeOH by the addition of one equivalent of NaOMe or LiOMe.
The resulting solution was then combined with a black-brown sus-
pension of [Ni(‘S3’)]3 (1) in THF and the mixture was stirred until
all the solid material had dissolved (ca. 30 min). One equivalent of
NBu4OH in MeOH was then added and all volatile components
were removed in vacuo. The residue obtained was taken up in THF
(ca. 20 mL), undissolved material was removed by filtration, and
the filtrate was concentrated to one-third of its original volume. On
layering with Et2O or n-hexane, black crystals precipitated, which
were separated after 4 d, washed with Et2O (60 mL), and dried
in vacuo.
[Ni(PR3)(‘S3’)], where R ؍ Cy (7), Ph (8) ؊ General Procedure: The
appropriate PR3 was added as a solid to a stirred black-brown THF
suspension of [Ni(‘S3’)]3 (1). In the course of few seconds, a deep-
red solution formed, which was filtered. Upon dropwise addition
of MeOH (ca. 20 mL), a dark-red solid precipitated, which was
separated, washed with MeOH (ca. 50 mL), and dried in vacuo.
[Ni(PCy3)(‘S3’)] (7): 665 mg (0.72 mmol) of 1; 841 mg (3.00 mmol)
of PCy3; 10 mL of THF. Yield: 1.16 g (91%). Ϫ C30H41NiPS3
(587.50): calcd. C 61.33, H 7.03, S 16.37; found C 61.47, H 7.29, S
16.23. Ϫ IR (KBr): ν˜ ϭ 1099 cmϪ1, δ(PCH). Ϫ 1H NMR
(270.6 MHz, CDCl3): δ ϭ 7.70 (d, 2 H, C6H4), 7.40 (d, 2 H, C6H4),
7.10 (m, 2 H, C6H4), 7.00 (m, 2 H, C6H4), 2.20Ϫ1.20 [m, 33 H,
P(C6H11)3]. Ϫ 13C{1H} NMR (67.7 MHz, CDCl3): δ ϭ 152.4 (d,
3JP,C ϭ 10.2 Hz), 132.2, 129.7, 128.2, 127.0, 122.2 (C6H4), 34.0 (d,
1JP,C ϭ 20.2 Hz), 30.0, 27.6 (d, JP,C ϭ 10.1 Hz), 26.4 [P(C6H11)3].
(NBu4)[Ni(StBu)(‘S3’)] (3): 1.685 g (1.83 mmol) of 1; 5.1 mL
(5.61 mmol) of a 1.1  solution of NaStBu in MeOH; 6.9 mL
(5.52 mmol) of a 0.8  solution of NBu4OH in MeOH; 30 mL of
THF. Yield: 1.858 mg (53%). Ϫ C32H53NNiS4 (638.71): calcd. C
60.18, H 8.36, N 2.19, S 20.08; found C 60.14, H 8.81, N 2.29, S
19.47. Ϫ 1H NMR (269.6 MHz, [D6]acetone): δ ϭ 7.67 (d, 2 H,
C6H4), 7.22 (d, 2 H, C6H4), 6.94 (m, 2 H, C6H4), 6.82 (m, 2 H,
C6H4), 3.48 (t, 8 H, NCH2), 1.77 (m, 8 H, NCH2CH2), 1.50 (s, 9
Ϫ
31P{1H} NMR (109.4 MHz, CDCl3): δ ϭ 28.3 [s, P(C6H11)3]. Ϫ
MS (FD, THF); m/z: 587 [Ni(PCy3)(‘S3’)]ϩ.
[Ni(PPh3)(‘S3’)] (8): 500 mg (0.54 mmol) of 1; 525 mg (2.00 mmol)
of PPh3; 5 mL of THF. Yield: 894 mg (97%). Ϫ C30H23NiPS3
(569.36): calcd. C 63.29, H 4.07, S 16.89; found C 63.47, H 4.17, S
H, SCCH3), 1.37 [m,
8 H, N(CH2)2CH2], 0.90 [t, 12 H,
16.51. Ϫ IR (KBr): ν ϭ 1094 cmϪ1, δ(PCH). Ϫ 1H NMR
˜
N(CH2)3CH3]. Ϫ 13C{1H} NMR (100.4 MHz, [D6]acetone): δ ϭ
158.0, 134.3, 129.8, 128.2, 128.0, 121.0 (C6H4), 59.4 (NCH2), 40.1
(SCCH3), 37.5 (SCCH3), 24.6, 20.3 [NCH2(CH2)2], 13.9
[N(CH2)3CH3].
(269.6 MHz, CDCl3): δ ϭ 7.82 (m, C6H5), 7.72 (d, 2 H, C6H4),
7.46 (m, C6H5), 7.28 (d, 2 H, C6H4), 7.07 (m, 2 H, C6H4), 7.01 (m,
2 H, C6H4). Ϫ 13C{1H} NMR (67.7 MHz, CD2Cl2): δ ϭ 152.8 (d,
3JP,C ϭ 5.7 Hz), 134.9 (d, JP,C ϭ 12.2 Hz), 132.6, 131.3, 130.0 (d,
1JP,C ϭ 48.0 Hz), 129.7, 129.0, 128.6 (d, JP,C ϭ 10.8 Hz), 127.8,
123.0 [C6H4, P(C6H5)3]. Ϫ 31P{1H} NMR (109.4 MHz, CDCl3):
δ ϭ 30.4 [s, P(C6H5)3].
(NBu4)[Ni(SCy)(‘S3’)] (4): 1.365 g (1.48 mmol) of 1; 8.84 mL
(4.42 mmol) of a 0.5  solution of NaSCy in MeOH; 4.44 mL
(4.44 mmol) of a 1.0  solution of NBu4OH in MeOH; 50 mL of
THF. Yield: 2.508 g (85%). Ϫ C34H55NNiS4 (664.78): calcd. C
61.43, H 8.34, N 2.11, S 19.29; found C 61.35, H 8.45, N 2.19, S
18.68. Ϫ 1H NMR (269.6 MHz, [D6]acetone): δ ϭ 7.65 (d, 2 H,
C6H4), 7.20 (d, 2 H, C6H4), 6.94 (m, 2 H, C6H4), 6.82 (m, 2 H,
C6H4), 3.49 (t, 8 H, NCH2), 2.43Ϫ1.10 [m, 27 H, NCH2(CH2)2,
(NBu4)[Ni(Cl)(‘S3’)] (9): [Ni(‘S3’)]3 (1) (1.660 g, 1.80 mmol) and
NBu4Cl (1.550 g, 5.41 mmol) were combined in THF (20 mL) and
the mixture was stirred at room temperature for 24 h to give a violet
suspension. This suspension was then cooled to Ϫ30°C, and the
precipitate was filtered off, washed with THF, and dried in vacuo.
Yield: 2.311 g (73%). Ϫ C28H44ClNNiS3 (584.99): calcd. C 57.49,
H 7.58, N 2.39, S 16.44; found C 56.98, H 7.68, N 2.36, S 16.54.
SC6H11], 0.90 [t, 12 H, N(CH2)3CH3].
Ϫ
13C{1H} NMR
(67.8 MHz, [D6]acetone): δ ϭ 157.2, 134.7, 129.8, 128.4, 128.1,
121.2 (C6H4), 69.3, 59.5, 39.9, 29.6, 29.4, 24.7, 20.4, 14.1
(SC6H11, NC16H36).
1
Ϫ H NMR (269.7 MHz, [D8]THF): δ ϭ 7.63 (d, 2 H, C6H4), 7.18
(d, 2 H, C6H4), 6.94 (m, 2 H, C6H4), 6.77 (m, 2 H, C6H4), 3.53 (t,
(NBu4)[Ni(SMe)(‘S3’)] (5): 369 mg (0.41 mmol) of 1; 12.32 mL
8 H, NCH2), 1.75 (m, 8 H, NCH2CH2), 1.38 [m, 8 H,
(1.23 mmol) of a 0.1  solution of LiSMe in MeOH; 1.50 mL N(CH2)2CH2], 0.90 [t, 12 H, N(CH2)3CH3]. Ϫ 13C{1H} NMR
276
Eur. J. Inorg. Chem. 2000, 271Ϫ279

Transition Metal Complexes with Sulfur Ligands, 139
(67.7 MHz, [D6]acetone): δ ϭ 153.9, 138.2, 131.7, 129.4, 129.0, Ϫ C29H44N2NiS4 (607.61): calcd. C 57.33, H 7.30, N 4.61, S 21.11;
FULL PAPER
122.3 (C6H4), 59.4, 24.8, 20.7, 14.1 (NC16H36).
found C 56.82, H 7.33, N 4.78, S 20.12. Ϫ IR (KBr): ν˜ ϭ 2105
cmϪ1, ν(NCS). Ϫ 1H NMR (269.6 MHz, [D6]acetone): δ ϭ 7.66
(d, 2 H, C6H4), 7.21 (d, 2 H, C6H4), 7.06 (m, 2 H, C6H4), 6.92 (m,
2 H, C6H4), 3.47 (t, 8 H, NCH2), 1.81 (m, 8 H, NCH2CH2), 1.45
[m, 8 H, N(CH2)2CH2], 0.95 [t, 12 H, N(CH2)3CH3]. Ϫ 13C{1H}
NMR (67.7 MHz, [D6]acetone): δ ϭ 153.3 (C6H4), 140.6 (NCS),
133.2, 129.3, 129.0, 128.0, 122.4 (C6H4), 59.2, 24.4, 20.2, 13.8
(NC16H36).
(NBu4)[Ni(N3)(‘S3’)] (10): A 1.0  THF solution of NBu4N3
(3.0 mL, 3.00 mmol) was added to a black-brown suspension of
[Ni(‘S3’)]3 (1) (900 mg, 0.97 mmol) in THF (10 mL). The reaction
mixture was stirred overnight at room temperature to give a violet
solution, which was then filtered. Layering of the filtrate with
(iPr)2O (10 mL) led to the precipitation of black-violet microcrys-
tals, which were separated, washed with (iPr)2O, and dried in va-
cuo. Yield: 1.364 g (79%). Ϫ C28H44N4NiS3 (591.55): calcd. C
56.85, H 7.50, N 9.47, S 16.26; found C 56.87, H 8.47, N 9.17, S
16.36. Ϫ IR (KBr): ν˜ ϭ 2035 cmϪ1, ν(N3). Ϫ 1H NMR
(269.7 MHz, [D8]THF): δ ϭ 7.56 (d, 2 H, C6H4), 7.19 (d, 2 H,
C6H4), 6.96 (m, 2 H, C6H4), 6.81 (m, 2 H, C6H4), 3.49 (t, 8 H,
NCH2), 1.75 (m, 8 H, NCH2CH2), 1.39 [m, 8 H, N(CH2)2CH2],
0.89 [t, 12 H, N(CH2)3CH3]. Ϫ 13C{1H} NMR (67.8 MHz,
[D8]THF): δ ϭ 154.9, 134.7, 129.7, 128.5, 128.3, 121.6 (C6H4), 59.6,
25.0, 20.7, 14.2 (NC16H36).
(NBu4)[Ni(NSO)(‘S3’)] (12): 1.00 g (1.57 mmol) of 3; 500 mg
(3.70 mmol) of Me3SiNSO; 20 mL of THF; volatile components
were removed after 2 d; orange powder. Yield: 824 mg (86%). Ϫ
C28H44N2NiOS4 (611.60): calcd. C 54.99, H 7.25, N 4.58, S 20.97;
found C 54.75, H 7.22, N 4.21, S 20.28. Ϫ IR (KBr): ν˜ ϭ 1230
cmϪ1
, , νsym(NSO). Ϫ
νasym(NSO), 1030 cmϪ1 1H NMR
(269.6 MHz, [D8]THF): δ ϭ 7.59 (d, 2 H, C6H4), 7.19 (d, 2 H,
C6H4), 6.95 (m, 2 H, C6H4), 6.81 (m, 2 H, C6H4), 3.41 (t, 8 H,
NCH2), 1.65 (m, 8 H, NCH2CH2), 1.35 [m, 8 H, N(CH2)2CH2],
0.85 [t, 12 H, N(CH2)3CH3]. Ϫ 13C{1H} NMR (67.8 MHz,
[D8]THF): δ ϭ 155.8, 134.1, 129.9, 128.4, 128.2, 121.5 (C6H4), 59.6,
25.0, 20.7, 14.2 (NC16H36).
؊
(NBu4)[Ni(X)(‘S3’)] from 3 and Me3SiX, where X ؍ Cl؊ (9), N3
(10), NCS؊ (11), NSO؊ (12) ؊ General Procedure: The appropriate
Me3SiX was added to a black-brown THF solution of (NBu4)[Ni-
(StBu)(‘S3’)] (3). A color change was observed within a period of
time ranging from 5 min up to 48 h depending on the Me3SiX com-
pound. All volatile components were then removed in vacuo, and
the residue obtained was extracted with Et2O (ca. 10 mL), sepa-
rated, washed with Et2O, and dried in vacuo.
(NBu4)[Pd(StBu)(‘S3’)] (13): A 1.1  MeOH solution of NaStBu
(0.74 mL, 0.81 mmol), NBu4Cl (220 mg, 0.80 mmol), and
[Pd(‘S3’)]3 (2) (290 mg, 0.27 mmol) were combined in THF
(10 mL). The resulting mixture was stirred at room temperature for
24 h to give a red solution. Undissolved material was removed by
filtration, and the red filtrate was concentrated to one-third of its
original volume. Layering with Et2O led to the precipitation of red
crystals, which were separated after 4 d, washed with Et2O (10 mL),
and dried in vacuo. Yield: 452 mg (81%). Ϫ C32H53NPdS4 (686.44):
calcd. C 55.99, H 7.78, N 2.04, S 18.68; found C 53.37, H 8.36, N
(NBu4)[Ni(Cl)(‘S3’)] (9): 250 mg (0.39 mmol) of 3; 0.10 mL
(1.07 mmol) of Me3SiCl; 3 mL of THF; volatile components were
removed after 30 min.; violet powder.
(NBu4)[Ni(N3)(‘S3’)] (10): 275 mg (0.43 mmol) of 3; 0.15 mL
(1.47 mmol) of Me3SiN3; 15 mL of THF; volatile components were
removed after 24 h; violet powder.
1
1.98, S 18.05. Ϫ H NMR (269.7 MHz, [D6]acetone): δ ϭ 7.64 (d,
2 H, C6H4), 7.25 (d, 2 H, C6H4), 6.97 (m, 2 H, C6H4), 6.85 (m, 2
(NBu4)[Ni(NCS)(‘S3’)] (11): 125 mg (0.20 mmol) of 3; 0.07 mL H, C6H4), 3.41 (t, 8 H, NCH2), 1.73 (m, 8 H, NCH2CH2), 1.46 (s,
(0.47 mmol) of Me3SiNCS; 3 mL of THF; volatile components
9 H, SCCH3) 1.38 [m, 8 H, N(CH2)2CH2], 0.90 [t, 12 H,
were removed after 5 min; dark-red powder. Yield: 114 mg (94%). N(CH2)3CH3]. Ϫ 13C{1H} NMR (100.4 MHz, [D6]acetone): δ ϭ
Table 3. Selected crystallographic data for [Ni(‘S3’)]3 · 3 THF · 6 MeOH (1 · 3 THF · 6 MeOH), [Pd(‘S3’)]3 · 2 CH2Cl2 (2 · 2 CH2Cl2),
(NBu4)[Ni(StBu)(‘S3’)] (3), (NBu4)[Ni(SCy)(‘S3’)] (4), and (NBu4)[Ni(SPh)(‘S3’)] (6)
Compound
1 · 3 THF · 6 MeOH
2 · 2 CH2Cl2
3
4
6
Formula
Mr [g/mol]
Crystal system
Space group
a [pm]
C54H72Ni3O9S9
1329.79
trigonal
P3(bar)
1851.0(7)
1851.0(7)
983.2(8)
90
C38H28Cl4Pd3S9
1234.14
triclinic
P1(bar)
951.6(6)
1462.7(10)
1593.7(12)
88.47(6)
77.90(5)
82.01(5)
2.148(3)
2
C32H53NNiS4
638.70
monoclinic
P21/n
C34H55NNiS4
664.74
orthorhombic
Pbca
C34H49NNiS4
658.69
monoclinic
C2/c
1059.1(3)
1931.8(3)
1717.8(5)
90
1005.4(2)
1608.9(9)
4352.5(9)
90
4474.6(9)
1024.3(2)
1590.4(3)
90
b [pm]
c [pm]
α [°]
β [°]
90
103.20(3)
90
90
90
107.70(3)
90
γ [°]
120
V [nm3]
Z
2.917(3)
2
3.422(2)
4
7.041(4)
8
6.944(2)
8
dcalcd. [g/cm3]
1.514
13.34
1.908
1.240
8.32
1.254
8.12
1.260
8.22
µ [cmϪ1
]
19.59
Cryst. size [mm3]
ω-scan [°/min]
2θ range [°]
0.5 ϫ 0.4 ϫ 0.4
8.0
0.3 ϫ 0.2 ϫ 0.1
10.0
0.7 ϫ 0.5 ϫ 0.4
10.0
0.4 ϫ 0.4 ϫ 0.1
3.0Ϫ30.0
6.1Ϫ54.0
5453
0.8 ϫ 0.4 ϫ 0.2
3.0Ϫ30.0
4.0Ϫ50.1
8680
4.0Ϫ54.0
5423
3.8Ϫ52.0
9400
4.1Ϫ52.0
8330
Measured refl.
Independent refl.
Observed refl.
ref. parameters
R1[a]; wR2 [%]
4145
8436
6710
5453
6136
1083
1487
3625
1024
2776
228
487
344
361
361
6.4; 17.5
7.4; 20.0
6.5; 19.5
2.9; 7.5
4.7; 10.7
[a]
[I > 2σ(I)].
Eur. J. Inorg. Chem. 2000, 271Ϫ279
277

D. Sellmann, F. Geipel, F. W. Heinemann
FULL PAPER
Table 4. Selected crystallographic data for [Ni(PCy3)(‘S3’)] · THF (7 · THF), [Ni(PPh3)(‘S3’)] · CDCl3 (8 · CDCl3), (NBu4)[Ni(Cl)(‘S3’)] (9),
and (NBu4)[Pd(StBu)(‘S3’)] (13)
Compound
7 · THF
8 · CDCl3
9
13
Formula
Mr [g/mol]
Crystal system
Space group
a [pm]
C34H49NiOPS3
659.59
orthorhombic
Pnma
C31H23Cl3DNiPS3
689.72
C28H44ClNNiS3
584.98
monoclinic
P21/n
C32H53NPdS4
686.39
orthorhombic
Pbca
monoclinic
P21/c
2275.1(7)
1713.1(4)
859.8(3)
90
1731.1(2)
922.5(1)
1883.4(3)
90
953.8(4)
1660.4(7)
1891.2(6)
90
1952.2(2)
1666.1(3)
2116.0(2)
90
b [pm]
c [pm]
α [°]
β [°]
90
90
95.4(1)
90
90.01(4)
90
90
90
γ [°]
V [nm3]
Z
3.351(2)
4
2.994(1)
4
2.995(2)
4
6.882(2)
8
dcalcd. [g/cm3]
1.307
8.39
1.530
12.00
1.297
9.63
1.325
8.03
µ [Ϫ1
]
Cryst. size [mm3]
ω-scan [°/min]
2θ range [°]
0.5 ϫ 0.5 ϫ 0.3
3.0Ϫ30.0
4.0Ϫ54.0
6237
0.6 ϫ 0.6 ϫ 0.6
3.0Ϫ30.0
4.0Ϫ54.0
6810
0.5 ϫ 0.3 ϫ 0.1
3.0Ϫ30.0
4.2Ϫ55.2
9724
0.4 ϫ 0.3 ϫ 0.1
3.0Ϫ30.0
4.2Ϫ52.0
8097
Measured refl.
Independent refl.
Observed refl.
ref. parameters
R1[a]; wR2 [%]
3787
6593
6922
6766
1882
4317
3644
2310
190
352
309
350
3.4; 7.4
3.6; 8.9
4.1; 11.0
4.0; 7.9
[a]
[I > 2σ(I)].
158.0, 134.2, 131.2, 129.6, 128.5, 121.4 (C6H4), 59.4 (NCH2), 41.7 refined. In the case of complex 9, the crystal under study proved
(SCCH3), 37.6 (SCCH3), 24.6, 20.4 [NCH2(CH2)2], 13.9
[N(CH2)3CH3].
to be a pseudomerohedral twin. The twin component ratio was
refined to give 0.694(1) and 0.306(1), respectively. Selected crystal-
lographic data are listed in Tables 3 and 4.[15]
X-ray Structure Analyses of [Ni(‘S3’)]3 ·3 THF·6 MeOH
(1·3 THF·6 MeOH), [Pd(‘S3’)]3 ·2 CH2Cl2 (2·2 CH2Cl2), (NBu4)-
[Ni(StBu)(‘S3’)] (3), (NBu4)[Ni(SCy)(‘S3’)] (4), (NBu4)[Ni-
(SPh)(‘S3’)] (6), [Ni(PCy3)(‘S3’)] · THF (7 · THF), [Ni(PPh3)-
(‘S3’)] · CDCl3 (8 · CDCl3), (NBu4)[Ni(Cl)(‘S3’)] (9), and (NBu4)-
[Pd(StBu)(‘S3’)] (13): Black hexagons of 1 · 3 THF · 6 MeOH were
grown by slow evaporation of the solvent at room temperature from
the THF/MeOH mother liquor resulting from the synthesis of
[Ni(‘S3’)]2.[6] Black single crystals of 2 · 2 CH2Cl2 were formed
upon layering a CH2Cl2 solution of 2 with Et2O. Black-red plates
of 3, 4, 6, and 13 were obtained directly from the respective reaction
solutions. Orange plates of 7 · THF were grown by layering a THF
solution of 7 with MeOH. Red-brown blocks of 8 · CDCl3 were
similarly grown by layering the CDCl3 solution of 8 that had been
used for NMR measurements with MeOH. Black plates of 9 were
grown by layering a THF solution of 9 with Et2O. In all cases,
suitable single crystals were sealed in glass capillaries under N2.
Data were collected at 200 K (1 · 3 THF · 6 MeOH, 3, 4, 6,
7 · THF, 8 · CDCl3, 9, 13) or 298 K (2 · 2 CH2Cl2) on a Siemens P4
or a Nicolet R3 m/V (2 · 2 CH2Cl2) diffractometer using graphite-
monochromated Mo-Kα radiation (λ ϭ 71.073 pm) by the ω-scan
technique. In the case of 2 · 2 CH2Cl2 and 3, an absorption correc-
tion was applied on the basis of ψ-scans. The structures were solved
by direct methods (SHELXTL-PLUS[14a] or SHELXTL 5.03[14b]).
Full-matrix least-squares refinement was carried out on F2
(SHELXL-93[14c] or SHELXTL 5.03[14b]). All non-hydrogen atoms
were refined anisotropically. The positions of the hydrogen atoms
in 3, 4, 6, 7 · THF, 8 · CDCl3, and 9 were taken from the difference
Fourier map and were kept fixed with a common isotropic displace-
ment parameter. In the case of 1 · 3 THF · 6 MeOH, 2 · 2 CH2Cl2,
and 13, the hydrogen atoms were geometrically positioned with iso-
tropic displacement parameters fixed at 1.5 times the U(eq) of the
adjacent carbon atom. One n-butyl group (C40ϪC43) in the cation
of 3 is evidently disordered, but no well-separated sites could be
Acknowledgments
Support of these investigations by the Deutsche Forschungsge-
meinschaft and the Fonds der Chemischen Industrie is gratefully
acknowledged.
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