Reactions of Di(1-cyclohepta-2,4,6-trienyl)sulfane, S(C7H 7)2, with derivatives of the hexacarbonyls, M(CO) 6 (M = Cr, Mo, W)

Article abstract of DOI:10.1002/zaac.200400196

Mononuclear carbonylmetal complexes of chromium, molybdenum and tungsten containing the sulfane S(C₇H₇)₂ (1) have been obtained starting from precursors such as the THF-stabilized pentacarbonylmetal fragments, [M(CO)₅](thf), the acetonitrile intermediates M(CO) _6-x(CH₃CN)_x (x = 1, 2, 3) (M = Cr, Mo, W) or the η⁴-norbornadiene complexes M(CO)₄(C ₇H₈) (M = Cr, Mo). In addition to the pentacarbonyls, M(CO)₅[S(C₇H₇)₂] (M = Cr (2a), Mo (2b), W (2c)) which contain 1 unchanged as a two-electron sulfane ligand with two pending cyclohepta-2,4,6-trienyl substituents, isomeric complexes M(CO) ₅[S(CH₂Ph)(C₇H₇)] (M = Cr (3a), W (3c)) were obtained at higher temperatures (40-50°C) in which one of the two organic groups has been transformed into a benzyl substituent. In the tetracarbonyls, cis-M(CO)₄[S(C₇H₇) (η²-C₇H₇)] (M = Mo (4b), W (4c)), the ligand 1 serves as an olefinic sulfane four-electron chelate ligand. The reaction of either Mo(CO)₆ or (mesitylene)Mo(CO)₃ with S(C₇H₇)₂ (1) in boiling THF leads to the sulfur-free ditropyl complex Mo(CO)₃[(η⁶-C ₇H₇)-C₇H₇] (5b, two isomers). The ¹H and ¹³C NMR spectra of the new complexes 2-4 reveal various dynamic processes including pyramidal inversion of the sulfur atom and [1,7]-sigmatropic shifts at the C₇H₇ ring. The molecular structures of 2c, 3a, 4b and 4c have been determined by X-ray crystallography.

Full text of DOI:10.1002/zaac.200400196

Reactions of Di(1-cyclohepta-2,4,6-trienyl)sulfane, S(C7H7)2, with Derivatives of
the Hexacarbonyls, M(CO)6 (M ؍ Cr, Mo, W)
Max Herberhold*, Jinnan Liu, Wolfgang Milius, Oleg Tok, Bernd Wrackmeyer
Bayreuth, Laboratorium für Anorganische Chemie der Universität
Received May 28th, 2004.
Dedicated to Professor Martin Jansen on the Occasion of his 60th Birthday
Abstract. Mononuclear carbonylmetal complexes of chromium,
molybdenum and tungsten containing the sulfane S(C7H7)2 (1)
have been obtained starting from precursors such as the THF-sta-
bilized pentacarbonylmetal fragments, [M(CO)5](thf), the aceto-
nitrile intermediates M(CO)6-x(CH3CN)x (x ϭ 1, 2, 3) (M ϭ Cr,
Mo, W) or the η4-norbornadiene complexes M(CO)4(C7H8) (M ϭ
Cr, Mo). In addition to the pentacarbonyls, M(CO)5[S(C7H7)2]
(M ϭ Cr (2a), Mo (2b), W (2c)) which contain 1 unchanged as a
two-electron sulfane ligand with two pending cyclohepta-2,4,6-tri-
enyl substituents, isomeric complexes M(CO)5[S(CH2Ph)(C7H7)]
(M ϭ Cr (3a), W (3c)) were obtained at higher temperatures
(40Ϫ50 °C) in which one of the two organic groups has been trans-
formed into a benzyl substituent. In the tetracarbonyls, cis-
M(CO)4[S(C7H7)(η2-C7H7)] (M ϭ Mo (4b), W (4c)), the ligand 1
serves as an olefinic sulfane four-electron chelate ligand. The reac-
tion of either Mo(CO)6 or (mesitylene)Mo(CO)3 with S(C7H7)2 (1)
in boiling THF leads to the sulfur-free ditropyl complex
Mo(CO)3[(η6-C7H7)-C7H7] (5b, two isomers). The 1H and 13C
NMR spectra of the new complexes 2Ϫ4 reveal various dynamic
processes including pyramidal inversion of the sulfur atom and
[1,7]-sigmatropic shifts at the C7H7 ring. The molecular structures
of 2c, 3a, 4b and 4c have been determined by X-ray crystallography.
Keywords: Chromium; Molybdenum; Tungsten; Sulfane complexes;
NMR spectra; Crystal structures
Umsetzungen von Di(1-cyclohepta-2,4,6-trienyl)sulfan, S(C7H7)2, mit Derivaten der
Hexacarbonyle, M(CO)6 (M ؍ Cr, Mo, W)
Inhaltsübersicht. Einkernige Carbonylmetall-Komplexe des
Chroms, Molybdäns und Wolframs mit dem Sulfan S(C7H7)2 (1)
wurden ausgehend von Vorstufen wie den THF-stabilisierten
Pentacarbonylmetall-Fragmenten, [M(CO)5](thf), den Acetonitril-
Zwischenstufen, M(CO)6Ϫx(CH3CN)x (x ϭ 1, 2, 3) (M ϭ Cr, Mo,
W) oder den η4-Norbornadien-Komplexen, M(CO)4(C7H8)
der beiden Organylgruppen als Benzyl-Substituent vorliegt. In den
Tetracarbonylen, cis-M(CO)4[S(C7H7)(η2-C7H7)] (M ϭ Mo (4b), W
(4c)) fungiert das olefinische Sulfan 1 als Vierelektronen-Chelat-
ligand. Die Reaktion von Mo(CO)6 oder (mesitylen)Mo(CO)3 mit
S(C7H7)2 (1) in siedendem THF führte zum schwefelfreien Ditro-
pyl-Komplex, Mo(CO)3[(η6-C7H7)-C7H7] (5b, zwei Isomere). Die
1H- und 13C-NMR-Spektren der neuen Komplexe 2؊4 lassen
verschiedene dynamische Prozesse erkennen, darunter pyramidale
Inversion am Schwefelatom und [1,7]-sigmatrope Verschiebungen
am C7H7-Ring. Die Molekülstrukturen von 2c, 3a, 4b und 4c im
Kristall wurden anhand von Röntgenstrukturanalysen bestimmt.
(M
ϭ Cr, Mo) dargestellt. Neben den Pentacarbonylen,
M(CO)5[S(C7H7)2] (M ϭ Cr (2a), Mo (2b), W (2c)), die 1 in unver-
änderter Form als Zweielektronen-Sulfanliganden mit zwei frei be-
weglichen Cyclohepta-2,4,6-trienyl-Substituenten enthalten, ent-
standen bei höherer Temperatur (40Ϫ50 °C) isomere Komplexe
M(CO)5[S(CH2Ph)(C7H7)] (M ϭ Cr (3a), W (3c)), in denen eine
Introduction
(M
ϭ
Cr, Mo, W) and of
a
dicarbonyl, cis-
Cr(CO)2[P(C7H7)(η2-C7H7)(η4-C7H7)], has led to com-
plexes in which the phosphane ligand [P(C7H7)3] may pro-
gressively act as a two-, four-, six- or eight-electron ligand,
although its basic structure remains intact.
Mononuclear derivatives of the hexacarbonyl metals,
M(CO)6 (M ϭ Cr, Mo, W), with the olefinic phosphane
ligand, tri(1-cyclohepta-2,4,6-trienyl) phosphane, P(C7H7)3,
have been characterized by 1H, 13C and 31P NMR spec-
troscopy [1]. The stepwise formation of pentacarbonyls,
M(CO)5[P(C7H7)3], tetracarbonyls, cis-M(CO)4[P(C7H7)2-
(η2-C7H7)], tricarbonyls, fac-M(CO)3[P(C7H7)2(η4-C7H7)]
The corresponding reactions with the olefinic sulfane,
di(1-cyclohepta-2,4,6-trienyl)sulfane, S(C7H7)2 (1), are more
limited in scope due to the lower thermal stability and pho-
tosensitivity of the thioether 1 [2]. For example, the photo-
induced reaction of Mn2(CO)10 with 1 produces the thio-
lato-bridged dimer, [Mn(CO)4(µ2-SC7H7)]2 [3], and com-
plete disintegration of 1 has been observed in the reaction
of the photo-generated fragment [CpMn(CO)2] with 1 to
give decomposition products such as [CpMn(CO)2]2-
(µ2-L) (L ϭ S and SO) [3]. Nevertheless, S(C7H7)2 (1) may
* Prof. Dr. M. Herberhold
Anorganisch-Chemisches Laboratorium der Universität
D-95440 Bayreuth
e-mail: max.herberhold@uni-bayreuth.de
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DOI: 10.1002/zaac.200400196
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Reactions of Di(1-cyclohepta-2,4,6-trienyl)sulfane, S(C7H7)2
also be incorporated into carbonylmetal complexes as an
intact ligand.
In the present study, we describe three types of Group 6
carbonylmetal
complexes:
the
pentacarbonyls
M(CO)5[S(C7H7)2] (2, M ϭ Cr (2a), Mo (2b) and W (2c))
with an intact di(1-cyclohepta-2,4,6-trienyl)sulfane ligand,
the pentacarbonyls M(CO)5[S(CH2Ph)(C7H7)] (3, M ϭ Cr
(3a), W (3c)) containing a partially rearranged sulfane
ligand, and the cis-tetracarbonyls cis-M(CO)4[S(C7H7)-
(η2-C7H7)] (4, M ϭ Mo (4b), W (4c)) involving a chelating
sulfane as a four-electron ligand. The molecular structures
of 2c, 3a, 4b and 4c were confirmed by X-ray crystallo-
graphy.
Synthesis and Spectroscopy
A reliable route to monosubstituted derivatives of the hexa-
carbonyl metals, M(CO)6, which contain 1 as an unchanged
two-electron ligand, involves the acetonitrile precursor
M(CO)5(CH3CN) (M ϭ Cr, Mo, W). Although up to 3 CO
ligands are stepwise replaced from M(CO)6 in boiling aceto-
nitrile to give M(CO)6Ϫx(CH3CN)x (x ϭ 1, 2, 3) [4,5], the
reaction can be terminated when the pentacarbonyl is the
dominant product in the mixture (after evolution of ca. 1.1
equivalent of CO).
40Ϫ50 °C, the benzyl complex W(CO)5[S(CH2Ph)(C7H7)]
(3c) is obtained directly. The corresponding photo-induced
reaction of Cr(CO)6 with 1 gives 3a even at room tempera-
ture.
The initial complexes (2a,c) may react further under iso-
merization of one 1-cyclohepta-2,4,6-trienyl to a benzyl
substituent to give 3a,c. In the case of M ϭ Mo and W, the
tetracarbonyls 4b,c are formed together with 2b,c. There-
fore, 2b,c were isolated from the reaction mixtures by
column chromatography on silica.
The tungsten complex 2c is also conveniently prepared
via the 1:1 reaction of the photo-generated intermediate,
[W(CO)5](thf), with the sulfane, S(C7H7)2 (1), in THF solu-
tion at room temperature. If the reaction is carried out at
The benzyl complexes 3a and 3c are clearly formed by
thermal isomerization of 2a and 2c, respectively.
Table 1 Spectroscopic data of the di(1-cyclohepta-2,4,6-trienyl)sulfane complexes 2aϪc
S(C7H7)2 (1) [3]
Cr(CO)5[S(C7H7)2] (2a)
(orange)
Mo(CO)5[S(C7H7)2] (2b)
(dark-yellow)
W(CO)5[S(C7H7)2] (2c)
(light-yellow)
1H NMR (CDCl3)
δ(H1)
3.61t (2H)
5.48m (4H)
6.22dt (4H)
6.58t (4H)
3.89t (2H)
5.52dd (4H)
6.38m (4H)
6.68s (4H)
3.92t (2H)
5.55m (4H)
6.38m (4H)
6.70t (4H)
4.02t (2H)
5.54m (4H)
6.41m (4H)
6.69t (4H)
δ(H2, H7)
δ(H3, H6)
δ(H4, H5)
13C NMR (CDCl3)
δ(C1)
41.6
47.6
48.0
49.7
δ(C2, C7)
124.7
126.4
131.2
121.3
128.7
132.0
215.2
221.3
121.9
128.6
131.8
204.7
211.5
121.8
128.9
131.9
197.3 [129.0]
199.5 [155.8]
δ(C3, C6)
δ(C4, C5)
δ(CO) (cis)
a)
b)
b)
δ(CO) (trans)
c)
IR: ν(CO) [cmϪ1
(pentane)
]
2075(w), 1951(s),
1941(m), 1928(m)
2075(w),1954(s),
1945(s), 1933(s)
2073(w), 1945(s),
1937(s), 1931(sh)
a) The complexes 2a-c consistently show two 13C NMR signals for the 5 CO ligands, the stronger peak corresponding to the 4 CO ligands cis to the sulfur
ligand appears at higher field, cf. Cr(CO)6 213.9, Mo(CO)6 201.0, W(CO)6 191.1.
b) Coupling constant, 1J(183W, 13C) [Hz].
c) Intensities: s strong, m medium, w weak, sh shoulder.
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M. Herberhold, J. Liu, W. Milius, O. Tok, B. Wrackmeyer
1
peratures (Fig. 2), the H resonances became broad, and
Table 2 Spectroscopic data of the (1-cyclohepta-2,4,6-trienyl)-
benzyl-sulfane complexes 3a and 3c
this indicates another dynamic process related to sigma-
tropic shifts at the cycloheptatrienyl ring. At low tempera-
ture, the pyramidal inversion is slowed down and most of
Cr(CO)5[S(CH2Ph)(C7H7)] W(CO)5[S(CH2Ph)(C7H7)]
(3a)
(3c)
the expected splittings in the H and 13C NMR spectra are
1
1H NMR (CDCl3)
δ(H1)
observed, as shown for the example of 2c in Figure 2. The
13C NMR spectra of 2c (Fig. 3), measured at room tem-
perature and below, are also in support of either fast or
slow inversion at the sulfur atom. At low temperature, the
4.16t (1H)
4.36t (1H)
δ(H2, H7)
δ(H3, H6)
δ(H4, H5)
δ(CH2)
5.69dd (2H)
6.43m (2H)
6.71dd (2H)
3.88s (2H)
5.72dd (2H)
6.50m (2H)
6.74dd (2H)
4.08s (2H)
1
benzylic H(CH2) NMR signal of 3c is split, showing the
δ(Ph)
7.18-7.30m (5H)
7.20-7.31m (5H)
characteristic pattern of an AB spin system (2J(1H,1H) ϭ
12.0 Hz), and from the coalescense of the signals at 230 K,
the activation energy of the barrier to inversion of the sulfur
atom can be evaluated [6] as ∆G# ϭ 46.5 1 kJmolϪ1. This
value is in the range described in numerous studies carried
out by other groups, in particular by Abel et al. [7Ϫ11].
13C NMR (CDCl3)
δ(C1)
51.0
121.6
129.5
132.0
53.2
121.9
129.6
132.1
δ(C2, C7)
δ(C3, C6)
δ(C4, C5)
δ(CH2)
43.3
45.5
128.2(p), 128.7(m),
129.6(o), 134.6(i)
214.9
128.3(p), 128.8(m),
129.7(o), 134.4(i)
197.0 [129.3] b)
199.9
δ(Ph) a)
δ(CO) (cis)
δ(CO) (trans)
221.3
c)
IR: n(CO) [cmϪ1
(pentane)
]
2068(w),
2073(w),
1945(s) / 1939(s) / 1930(m) d) 1941(s) / 1935(s) / 1929(s) d)
a) The tentative assignments of the o- and m-carbon signals correspond to
that in the 13C NMR spectrum of dibenzyl sulfide, cf. http://www.aist.go.jp
b) Coupling constant, 1J(183W, 13C) [Hz].
c) Intensities: s strong, m medium, w weak; cf. Cr(CO)6 1987 cmϪ1, W(CO)6
1984 cmϪ1
.
d) Broad absorption.
The characteristic spectroscopic data of the pentacar-
bonyl complexes 2aϪc and 3a,c at room temperature are
collected in Tables 1 and 2. Compared with the uncoordi-
Fig. 1 13C NMR spectrum of Cr(CO)5[S(CH2Ph)(C7H7)] (3a) at
room temperature.
1
nated sulfane, S(C7H7)2 (1), the H and 13C NMR patterns
of the freely pending cyclohepta-2,4,6-trienyl substituents
appear to be essentially unchanged, only the signals of the
protons H1 and of the carbon atoms C1 (connected with
the sulfur atom) are slightly shifted to higher frequencies,
the effect being more pronounced in the cases of 3a,c than
of 2aϪc. The assignment of the benzyl and cyclohepta-
2,4,6-trienyl 13C NMR signals of 3a,c (Fig. 1) is based on
2D 13C/1H HETCOR experiments. The pentacarbonylmetal
structure is evident from the two 13C carbonyl NMR signals
in the range of δ ϭ 195Ϫ225; the signal of lower intensity
(due to the CO group trans to the sulfane ligand) is ob-
served at higher frequency relative to the main signal (due
to the four CO groups cis to the sulfane). At a first glance,
the NMR spectra of the complexes of type 2 and 3, meas-
ured at room temperature, seem to indicate a rigid SϪM
coordination and the absence of fast fluxional processes.
However, if pyramidal inversion of the sulfur atom is slow,
all pairs of olefinic CH units in 2 should be diastereotopic,
and in 3, the benzylic CH2 hydrogen atoms should also be
diastereotopic as well as the olefinic CH units. Since these
features are not observed, it must be concluded that inver-
sion of the coordinated sulfur atom occurs fast when com-
pared with the NMR time scale. Furthermore, when the
1H NMR spectrum of 2c was measured at elevated tem-
Fig. 2 250 MHz 1H NMR spectra of W(CO)5[S(C7H7)2] (2c) at
various temperatures. A (220 K): The 1H NMR signals for H2,7
start to split, and the signals for H3,6 are split due to chemical non-
1
equivalence. B (room temperature): The H NMR spectrum looks
1
deceptively simple. C (323 K): Broadening of all H NMR signals
is observed indicating dynamic processes; the sharp signals are the
result of decomposition and can arise from the formation of
C7H7-C7H7.
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Reactions of Di(1-cyclohepta-2,4,6-trienyl)sulfane, S(C7H7)2
Fig. 3 125.8 MHz 13C{1H} NMR spectra of W(CO)5[S(C7H7)2]
(2c) at room temperature (A) and at 230 K (B). The spectrum in A
looks deceptively simple and 183W satellites are visible for the
13C(CO) NMR signals, as marked in the expansion. In B, the 13C
NMR signals for carbon atoms C2,7, C3,6 are split and that for C4,5
is broad at low temperature because of chemical non-equivalence,
when the pyramidal inversion of the sulfur atom becomes slow.
1
Fig. 4 Contour plot of the 250 MHz 2D H/1H EXSY spectrum,
measured for W(CO)5[S(C7H7)2] (2c) at room temperature using a
mixing time of 0.2 s. The off-diagonal cross peaks indicate the ex-
change via [1,7]-sigmatropic rearrangements, the more intensive
ones corresponding to fast [1,7]-migration of the sulfur around the
seven-membered ring. The marked off-diagonal cross peaks with
lower intensities arise from two subsequent migrations of the same
type. A mixing time of 0.1 s leads to suppression of these cross
peaks, whereas a mixing time of 0.5 s shows additional cross peaks
for the third and further rearrangements.
The [1,7]-sigmatropic rearrangement [12Ϫ14] indicated
by the high-temperature NMR spectrum of 2c (Fig. 2) is
clearly visualized by the results of two-dimensional (2D)
1H/1H EXSY NMR experiments [15], (Fig. 4).
Whereas
the
photo-generated
intermediates
[M(CO)5](thf) (M ϭ Cr, W) react with S(C7H7)2 (1) in THF
solution to give pentacarbonylmetal complexes (2c and 3a,c),
the corresponding molybdenum precursor [Mo(CO)5]-
(thf) leads immediately to the tetracarbonyl chelate com-
plex, cis-Mo(CO)4[S(C7H7)(η2-C7H7)] (4b), which is also
accessible via the norbornadiene intermediate Mo(CO)4-
(η4-C7H8) [18].
The first and the second step of the [1,7]-sigmatropic
movement of the sulfur-containing group around the C7H7
ring can be observed. The appearance of the cross peaks
(Fig. 4) in the contour plot (with the same phase as the
diagonal peaks), depending in their intensities on the re-
spective mixing times, indicates the exchange, and the rate
constant for the [1,7]-sigmatropic shift can be evaluated [16]
by integration of the cross peaks as k ϭ 4.5 0.5 sϪ1. Inter-
estingly, in the free ligand 1, this process takes place much
more slowly, since 1D magnetization transfer 1H/1H experi-
ments did not show effects of exchange. The exchange is
also slow in PhS(C7H7), the S-phenyl derivative of 1, for
which a value of k ϭ 6.5 sϪ1 has been determined at
100 °C [17].
The IR spectra of 2a؊c and 3a,c (in pentane solution)
show the typical pentacarbonyl metal structure with 4 ab-
sorptions (Table 1 and 2), and the molecular size of the
isomeric chromium complexes 2a and 3a was also con-
firmed by observation of the respective molecular ion
(m/e ϭ 406) in the field-desorption mass spectra (FD-MS).
The analogous tungsten complex, W(CO)4[S(C7H7)-
(η2-C7H7)] (4c), was obtained (together with a minor
amount of 2c) from the reaction of the mixture of aceto-
nitrile precursors, W(CO)6-x(CH3CN)x (x ϭ 1, 2, 3), with
S(C7H7)2 (1). Attempts to prepare the tetracarbonyl chelate
complex of chromium (4a) were not successful. Both
[Cr(CO)5](thf) and Cr(CO)4(η4-C7H8) [18] gave 3a, and ir-
radiation of 2a resulted in photo-induced decomposition in-
stead of CO substitution.
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M. Herberhold, J. Liu, W. Milius, O. Tok, B. Wrackmeyer
Table 3 Spectroscopic data of the chelate complexes 4b and 4c
Mo(CO)4[S(C7H7)(η2-C7H7)] (4b)
25 °C
W(CO)4[S(C7H7)(η2-C7H7)] (4c)
-20 °C
25 °C
1H NMR (CDCl3)
δ(H1)
3.89t [7.9] (1H)
4.82t [8.1] (1H)
5.60m (2H)
3.92t (1H)
4.94t (1H)
5.38br (2H)
4.01t (1H)
4.96t (2H)
5.34m (2H)
δ(H1’)
δ(H4’, H5’)
3 multiplet groups
5.60m (4H)
6.47m (2H)
6.67m (4H)
5.59m (4H)
6.48m (2H)
6.68m (4H)
5.68-5.46m (4H)
6.59-6.49m (2H)
6.80-6.62m (4H)
13C NMR (CDCl3)
δ(C1)
42.6
47.3
84.6
43.7
48.2
77.2; 76.2
43.2
47.9
76.8; 76.0
δ(C1’)
δ(C4’, C5’)
Remaining 10 signals
(partially broadened)
(partially broadened)
132.68; 132.65; 131.8;
131.0; 130.0; 129.7; 126.1;
124.8; 123.7; 120.8
a)
213.8;
213.5
203.6 [166.1]
203.3 [168.1]
203.8; 203.3;
202.1; 198.8
δ(CO)
b)
IR: ν(CO) [cmϪ1
(pentane)
]
2034(m), 1945(s),
1931(s), 1898(s)
2032(m), 1942(s),
1927(s), 1896(s)
a) Coupling constant, 1J(183W, 13C) [Hz].
b) Intensities: s strong, m medium.
The spectroscopic data for the tetracarbonyl chelate com-
plexes 4b and 4c are given in Table 3. The assignment of
1H and 13C NMR signals is based on 2D 1H/13C HETCOR
experiments, intensity data and comparison with the related
tetracarbonyl chelate complexes of the phosphane,
M(CO)4[P(C7H7)2(η2-C7H7)] (M ϭ Cr, Mo, W) [1]. In the
1H NMR spectra of 4b and 4c, the expected presence of 14
protons of the sulfane ligand was confirmed, although only
the pseudotriplets of H1 and H1’ have been unequivocally
assigned; the signal of proton H1’ of the coordinated C7H7
substituent undergoes a larger shift to higher frequencies
than that of the freely-pending substituent (H1), if com-
pared to the chemical shift of H1 in the uncoordinated thi-
oether 1 (δ(H1) ϭ 3.61, cf. Table 1). The complex dynamic
situation in the compounds 4b and 4c becomes apparent by
the broadened 13C NMR signals (at room temperature) of
the sulfane ligand and by the observation of only two
13C(CO) signals in equal intensity which, in the case of 4c,
are accompanied by 183W satellites due to 183W-13C spin-
spin coupling. In addition to the dynamic processes de-
scribed for the complexes 2 and 3 (vide supra) it is conceiv-
able that a third process is also involved, namely the ex-
change between the η2-coordinated and the pending C7H7
groups. This was not investigated in detail. However, at
Ϫ20 °C, the 13C NMR spectrum of 4c shows 18 sharp sig-
nals for all individual carbon atoms, i.e. 14 signals for the
sulfane ligand and 4 13C(CO) signals of equal intensity. The
1H and 13C NMR signals of the coordinated double bond
(H4’,5’ and C4’,5’) are shifted to low frequencies as a result
of π-complexation, as compared with the corresponding
signals of freely pending C7H7 rings in both 4b,c and in 1.
The IR spectra of 4b and 4c (in pentane solution) reveal the
characteristic cis-tetracarbonylmetal pattern with 4 ν(CO)
absorptions (Table 3).
In the series of carbonylmolybdenum complexes, an at-
tempt was made to prepare a tricarbonyl complex contain-
ing a η6-coordinated sulfane ligand, i.e. the unknown
sulfane
complexes
Mo(CO)3[(η6-C7H7)S(C7H7)]
or
S[(η6-C7H7)Mo(CO)3]2, related to the phosphane com-
pound P[(η6-C7H7)Mo(CO)3]3 [19].
However, if either Mo(CO)6 or (mesitylene)Mo(CO)3
were heated in refluxing THF solution in the presence of
S(C7H7)2 (1), loss of sulfur and formation of the ditropyl
complex 5b was observed. The mixture of endo-hydrogen
and exo-hydrogen (H1 and H1’, resp.) isomers of 5b can be
separated by thin-layer chromatography (TLC). The endo-
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Z. Anorg. Allg. Chem. 2004, 630, 2438Ϫ2449

Reactions of Di(1-cyclohepta-2,4,6-trienyl)sulfane, S(C7H7)2
form had been obtained previously [20] from Mo(CO)6
and ditropyl.
Studies on the dinuclear, ditropyl-bridged complexes,
[Mo(CO)3]2[µ-(η6-C7H7)2] (endo and exo isomers) are also
reported in the literature [20,21].
X-Ray Crystal Structure Analyses
The molecular structures of the two pentacarbonylmetal
sulfane complexes Cr(CO)5[S(CH2Ph)(C7H7)] (3a) and
W(CO)5[S(C7H7)2] (2c) are presented in Figures 5 and 6.
Bond distances are given in Table 4, bond angles and a few
characteristic dihedral angles are collected in Table 5.
Fig.
6
Molecular structure (50% probability ellipsoids) of
W(CO)5[S(C7H7)2] (2c)
Table 4 Bond distances /pm in the pentacarbonylmetal sulfane
complexes 3a (M ϭ Cr) and 2c (M ϭ W)
Cr(CO)5[S(CH2Ph)(C7H7)]
(3a)
W(CO)5[S(C7H7)2]
(2c)
M-S
242.68(16)
184.0(7)
189.6(7)
189.3(7)
188.4(7)
190.6(7)
257.32(10)
197.3(4)
204.7(4)
203.8(4)
204.0(4)
203.3(5)
M-C(15)
M-C(16)
M-C(17)
M-C(18)
M-C(19)
Fig.
5
Molecular structure (50% probability ellipsoids) of
Cr(CO)5[S(CH2Ph)(C7H7)] (3a)
S-C(1)
S-C(8)
186.3(5)
183.1(6)
182.6(4)
187.3(4)
In both 3a and 2c the pseudo-octahedral coordination
sphere of the metal contains a monodentate sulfane donor
ligand. The distance between the metal and the CO ligand
trans to sulfur (M-C(15)) is reduced by 5Ϫ7 pm as com-
pared with the average bond lengths between the metal and
the four cis-carbonyl ligands. This structural “trans-influ-
ence” of the sulfur-coordinated ligand is generally observed
in pentacarbonylchromium complexes, unless the ligand it-
self is a π-acceptor (like, e.g., SO2 [22]). For comparison,
Table 6 gives the metal carbonyl distances in [Cr(CO)5]- and
[W(CO)5] complexes with sulfur-containing ligands, to-
gether with the metal-sulfur bond lengths. In line with the
special role of the trans-carbonyl group, the shortened
MϪC(15) bond length (184.0(7) pm in 3a, 197.3(4) pm in
2c) is associated with a significantly lengthened C(15)ϪO(1)
bond (116.7(7) pm in 3a, 116.3(5) pm in 2c), as compared
with the CϪO bond distances of the four cis-carbonyl li-
gands (av. 113.7(7) pm in 3a, av. 113.8(5) pm in 2c), and the
angle MϪC(15)ϪO(1) (178.4(6)° in 3a, 178.6(4)° in 2c) is
O(1)-C(15)
O(2)-C(16)
O(3)-C(17)
O(4)-C(18)
O(5)-C(19)
116.7(7)
112.9(7)
113.9(7)
115.0(7)
113.1(7)
116.3(5)
113.6(5)
114.1(5)
113.8(5)
113.6(6)
C(1)-C(2)
C(1)-C(7)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
C(6)-C(7)
C(8)-C(9)
C(8)-C(14)
C(9)-C(10)
C(9)-C(14)
C(10)-C(11)
C(11)-C(12)
C(12)-C(13)
C(13)-C(14)
147.7(9)
146.8(9)
149.5(6)
150.0(5)
133.5(6)
142.5(8)
133.3(8)
145.6(8)
133.3(6)
131.5(7)
150.2(6)
149.9(6)
132.6(12)
137.1(16)
134.9(17)
145.8(16)
128.4(11)
150.6(7) a)
137.6(8) a)
136.5(8) a)
138.8(9) a)
136.0(10) a)
136.5(10) a)
138.8(9) a)
140.9(8)
131.6(8)
142.4(9)
135.2(8)
a) Benzyl substituent.
Z. Anorg. Allg. Chem. 2004, 630, 2438Ϫ2449
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 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
2443

M. Herberhold, J. Liu, W. Milius, O. Tok, B. Wrackmeyer
Table 5 Angles /° in the pentacarbonylmetal sulfane complexes
3a (M ϭ Cr) and 2c (M ϭ W)
Table 6 Metal-sulfur and metal-carbonyl bond distances in
[Cr(CO)5]- and [W(CO)5] complexes with sulfur-containing ligands
Cr(CO)5[S(CH2Ph)(C7H7)] W(CO)5[S(C7H7)2]
Cr(CO)5[L]
Cr-S
Cr-CO (trans) Cr-CO (cis) Ref.
(3a)
(2c)
L ϭ SO2 (A)
219.2(6) 187.3(17)
218.3(6) 190.0(17)
av. 189.7(13) [22]
av. 190.0(15)
av. 190.9(3) [23]
C(15)-M-C(16)
C(15)-M-C(17)
C(15)-M-C(18)
C(15)-M-C(19)
C(16)-M-C(17)
C(16)-M-C(18)
C(16)-M-C(19)
C(17)-M-C(18)
C(17)-M-C(19)
C(18)-M-C(19)
89.2(3)
87.92(16)
(B)
a)
89.0(3)
87.5(3)
90.4(3)
90.6(3)
176.3(3)
89.9(3)
90.9(3)
179.2(3)
88.5(3)
87.65(16)
88.80(16)
89.80(17)
94.53(18)
172.84(16)
88.61(18)
91.69(16)
175.88(15)
85.02(17)
S(ϭO)[CH2CH]2
SϭCMe2
233.1
185.8(5)
b)
237.7(4) 183.5
241.2(1)
av. 189.8
[24]
[25]
[26]
SϭC(Ph)Fc
SϭC(S)Pet3
SϭN-NMe2
SϭN-NPh2
S(Ph)N(CH2Ph)2 (A)
(B)
238.9(4) 178(2)
238.6(1) 184.6(2)
235.7(2) 184.8(7)
240.9(2) 181.2(7)
239.6(2) 181.6(10)
244.5(1) 183.0(4)
244.1(2) 184.4(4)
242.68(16) 184.0(7)
245.8(2) 185.9(7)
242.41(5) 185.7(2)
243.8(1) 184.1(4)
243.9(2) 182.8(8)
251.0(2) 181.5(8)
251.0(3) 182.7(10)
252.2(3) 180(1)
av. 186(2)
av. 190.3(5) [27]
av. 190.0(9) [27]
av. 187.1(8) [28]
av. 186.3(11)
S(Ph)NCy2
av. 188.5(5)
av. 188.8(4)
[29]
C(15)-M-S
C(16)-M-S
C(17)-M-S
C(18)-M-S
C(19)-M-S
175.5(2)
87.84(19)
87.6(2)
95.6(2)
93.0(2)
177.55(11)
94.23(11)
91.00(11)
89.20(11)
91.44(12)
S(CH2Ph)(C7H7)
S(CH2Ph)(Et)
S[CMe2]2COc)
av. 189.5(7) [A]
av. 187.9(10) [30]
av. 191.2(1) [31]
av. 191.2(4) [32]
av. 192.3(8) [33]
av. 190.0(4) [34]
av. 188.5(12) [35]
d)
SϭC[OCMe2]2
S(H)(tBu)
SϭPMe3
SϭC[N(Me)CH2]2
e)
C(1)-S-M
C(8)-S-M
C(1)-S-C(8)
112.8(2)
111.2(2)
98.4(3)
112.71(12)
108.35(13)
98.31(18)
S(SnMe3)2
av. 190(2)
[36]
cf.
{Cr(CO)5[SH]}Ϫ
247.3(2) 189.8(5)
247.9(1) 182.4(4)
av. 190.5(5) [37]
av. 188.1(6) [38]
S-C(1)-C(2)
S-C(1)-C(7)
111.1(4)
110.0(4)
110.0(6)
123.9(8)
127.5(10)
128.5(12)
121.6(11)
128.5(9)
125.5(7)
115.0(3)
111.1(3)
108.7(3)
119.8(4)
125.1(5)
125.9(5)
126.4(4)
124.4(5)
119.7(4)
111.3(3)
{Na(2.2.1-crypt)}ϩ
{Cr(CO)5[StBu]}Ϫ
{PPN}ϩ
C(2)-C(1)-C(7)
C(1)-C(2)-C(3)
C(2)-C(3)-C(4)
C(3)-C(4)-C(5)
C(4)-C(5)-C(6)
C(5)-C(6)-C(7)
C(6)-C(7)-C(1)
S-C(8)-C(9)
{[Cr(CO)5]2[StBu]}Ϫ
{PPN}ϩ
250.9(1) 183.4(5)
251.8(1) 182.2(6)
av. 189.2(5) [38]
av. 188.9(5)
W(CO)5[L]
W-S
W-CO (trans) W-CO (cis) Ref.
a)
L ϭ SϭC(H)Ph f)
SϭCH-C(Ph)ϭC(OEt)Ph
S4(NH)4
247.9(3) 200(1)
250.8(5)
252.5(2) 197(1)
[39]
[40]
[41]
110.2(4)
109.0(3)
111.0(4)
S-C(8)-C(14)
C(9)-C(8)-C(14)
C(8)-C(9)-C(10)
C(8)-C(9)-C(14)
C(10)-C(9)-C(14)
C(9)-C(10)-C(11)
C(10)-C(11)-C(12)
C(11)-C(12)-C(13)
C(12)-C(13)-C(14)
C(13)-C(14)-C(9)
C(13)-C(14)-C(8)
av. 203(1)
120.4(6) a)
120.4(5) a)
119.2(6) a)
119.9(6) a)
119.9(7) a)
121.1(7) a)
118.6(7) a)
121.3(7) a)
124.2(5)
126.0(4)
SϭC
T
C(Ph)C(Ph)S
US
252.8(6)
[42]
S[N(SiMe3)BMe]2NH g)
253.3(2) 196.5
254.8(2) 200.4(18)
255.3(6) 192(3)
255.3(7) 187(3)
201.7-205.6 [43]
av. 206.3(17) [44]
SϭC(OH)Me
127.3(4)
127.1(6)
126.7(6)
127.3(5)
av. 197(3)
av. 202(3)
[45]
h)
S3(CHMe)3
i)
T
S(CH2)2N(H)C(O)C
U
U
H2
255.1(14) 200.0(18)
255.6(8) 195(2)
255.5(2) 197.2(9)
av. 204.3(17) [46]
av. 204.5 [47]
j)
T
S(CH2)2N(H)C(S)C
H2
S(CH3)[C(SMe)-PPh2Me]
SϭC(N(H)(CH2)2
S) k)
SϭC[CHCH]2NH
av. 203.4(9) [48]
T
U
256(0.6) 197(2)
256.8(2) 196.0(6)
256.8(2) 197.6(8)
av. 202.5(20) [49]
av. 203.7(9) [50]
av. 203.7(9) [51]
M-C(15)-O(1)
M-C(16)-O(2)
M-C(17)-O(3)
M-C(18)-O(4)
M-C(19)-O(5)
178.4(6)
176.1(6)
176.7(6)
177.5(6)
177.7(6)
175.1(4)
178.6(4)
175.1(4)
177.4(4)
174.4(3)
l)
m)
SϭC(NH2)N(H)NϭCMe2
{S-C(S)OEt}Ϫ n)
{PPh4}ϩ
257.1(3) 194.5(13)
av. 204.5(14) [52]
S(tBu)(CH2StBu)
S(C7H7)2
257.1(5) 196.5(13)
257.32(10) 197.3(4)
257.9(2) 196.1(6)
259.6(2) 195.3(6)
261.7(2) 195.6(6)
262.2(5) 194(2)
av. 203.0(14) [53]
av. 204.0(5) [A]
[39]
av. 201.9(7) [54]
av. 203.1(8) [35]
S-CH(Ph)(PMe3) o)
b)
Dihedral angles
α
S(tBu)Sb(StBu)2
α1 45.3 (ax)
β1 22.6
α1 56.4 (eq)
α8 42.8 (ax)
β1 26.8
β8 21.5
147.5
e)
SϭC[N(Me)CH2]2
S(GeMe3)2
av. 204(2)
[36]
β
[A] This work.
a) 2,5-Dihydrothiophene-1-oxide; thioacetone; 2,2,4,4-tetramethyl-3-thi-
C(1)SC(8)/MS
C(16)MC(17)/C(18)MC(19) 3.4
145.1
b)
c)
4.3
d)
e)
etanone;
dazolidine-2-thione;
silyl)-1-thia-2,4,6-triaza-3,5-diborinane;
4,4,5,5-tetramethyl-1,3-dioxolan-2-thione; N,N’-dimethyl-imi-
f) g)
thiobenzaldehyde;
3,5-dimethyl-2,6-bis(trimethyl-
i)
a) Benzyl substituent.
h)
2,4,6-trimethyl-1,3,5-trithian;
b) cf. Fig. 7. The numbering (α1, β1 and α8, β8) refers to the cyclohepta-2,4,6-
j)
k)
l)
thiomorpholin-3-one; thiomorpholin-3-thione;
pyridine-2(1H)thione;
thiazolidine-2-thione;
trienyl ring containing the carbon atoms C(1) or C(8), respectively.
m)
n) o)
acetone-thiosemicarbazone;
xanthate;
(α-tri-
methylphosphonio)benzyl thiolate.
slightly larger than the average value for the four cis-car-
bonyl ligands (av. 175.5° in 3a, 177.0° in 2c). The four cis-
carbonyl ligands and the metal are essentially coplanar; the
dihedral angles, e.g. C(16)MC(17)/C(18)MC(19) (3.4° in 3a,
4.3° in 2c), are small.
According to Table 6, CrϪS distances between 218 and
253 pm have been reported for [Cr(CO)5] complexes with
various sulfur-containing ligands. The CrϪS bond length
determined for Cr(CO)5[S(CH2Ph)(C7H7)] (3a) (242.68(16)
pm) falls into the typical range (240Ϫ246 pm) of [Cr(CO)5]
2444
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2004, 630, 2438Ϫ2449

Reactions of Di(1-cyclohepta-2,4,6-trienyl)sulfane, S(C7H7)2
compounds with amino sulfanes, S(Ph)NR2 (R ϭ CH2Ph
[28], C6H11 [29]), thioalcohols (tBuSH [33]) and thioethers
(S(CH2Ph)Et [30]), cf. Table 6. In a similar manner, the
WϪS bond length in W(CO)5[S(C7H7)2] (2c) (257.32(10)
pm) is almost identical with that in the thioether complex,
W(CO)5[S(tBu)(CH2StBu)] (257.1(5) pm [53]). In general,
the WϪS distances in [W(CO)5] complexes of sulfur-con-
taining ligands are observed in the range of 247Ϫ262 pm,
cf. Table 6.
The 1-cyclohepta-2,4,6-trienyl substituent in the crystals
of 3a carries the sulfur atom in an axial position. In 2c only
one C7H7 substituent has the axial conformation, the other
assumes the (more spherical) equatorial conformation with
larger dihedral angles α and β, as defined in Figure 7. In
the uncoordinated sulfane 1, both C7H7 substituents are
axial [3]. It can be assumed that the axial or equatorial con-
formation of the 1-cyclohepta-2,4,6-trienyl substituents in
the crystal are determined by the steric situation in the
lattice. There is only a very small difference in energy (0.9
kJmolϪ1) between the axial and equatorial isomers of
C7H7-SH, with the axial isomers being slightly more stable,
according to calculations on the B3LYP/6-311ϩG(d,p) level
of theory [Gaussian 03 program package].
Fig.
8
Molecular structure (50% probability ellipsoids) of
W(CO)4[S(C7H7)(η2-C7H7)] (4c)
Table 7 Bond distances /pm in M(CO)4[S(C7H7)(η2-C7H7)]
(M ϭ Mo (4b) and W (4c))
M ϭ Mo (4b)
M ϭ W (4c)
M-S
253.8(3)
252.85(11)
246.0(5)
247.0(5)
199.1(6)
202.8(5)
195.7(5)
202.1(5)
M-C(4)
M-C(5)
M-C(15)
M-C(16)
M-C(17)
M-C(18)
250.2(10)
248.6(10)
196.1(13)
203.2(14)
195.6(12)
201.6(13)
Fig. 7 Conformation of the 1-cyclohepta-2,4,6-trienyl substituent
The
isostructural
cis-tetracarbonyl
complexes
M(CO)4[S(C7H7)(η2-C7H7)] (M ϭ Mo (4b) and W (4c))
crystallize in the monoclinic space group P21/c. The unit
cell which contains 4 molecules is slightly (ca. 1%) smaller
in the case of 4c, i.e. the tungsten-containing complex mol-
ecules 4c are marginally more compact than their molyb-
denum analogues 4b. The molecular geometry of the tung-
sten complex 4c with the numbering scheme is presented in
Fig. 8; the bond distances and angles are collected in Tables
7 and 8, respectively.
O(1)-C(15)
O(2)-C(16)
O(3)-C(17)
O(4)-C(18)
115.7(12)
115.1(13)
115.2(12)
114.3(13)
113.0(7)
113.4(6)
116.3(6)
114.8(7)
S-C(1)
S-C(8)
186.2(10)
186.5(10)
185.2(5)
186.0(5)
C(1)-C(2)
C(1)-C(7)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
C(6)-C(7)
C(8)-C(9)
C(8)-C(14)
C(9)-C(10)
C(10)-C(11)
C(11)-C(12)
C(12)-C(13)
C(13)-C(14)
149.0(15)
148.8(14)
132.1(15)
143.5(15)
138.8(15)
143.4(15)
133.4(15)
149.5(16)
148.9(14)
126.0(18)
145.0(2)
148.8(7)
151.2(7)
130.6(7)
146.7(7)
138.6(8)
145.8(8)
131.7(8)
147.5(7)
148.2(7)
133.8(10)
142.3(11)
134.1(11)
143.8(10)
131.7(8)
The pseudo-octahedral coordination sphere of 4b,c con-
tains two types of CO ligands, on the one hand the CO
groups trans to the sulfur (C(17)ϪO(3)) and to the coordi-
nated double bond (C(15)ϪO(1)), on the other hand the
CO groups cis to the ligand positions (C(16)ϪO(2) and
C(18)ϪO(4)). The distance between the metal and the
“trans” carbonyl ligands is significantly shortened as a
result of the structural “trans-influence”, and the angle
MϪCϪO is close to linearity (ca. 179°). The two “cis” car-
bonyl ligands (MϪC ca. 202 pm, MϪCϪO ca. 174°) in-
clude an angle C(16)ϪMϪC(18) of 169.4(5)° (4b) or
169.5(2)° (4c). The three CO ligands in the equatorial plane
(which is defined by the metal and the carbon atoms C(4),
134.0(2)
143.0(19)
132.8(16)
C(5), C(15), C(16), C(18)) are slightly pushed upwards by
the sulfane ligand towards the trans-carbonyl, C(17)ϪO(3).
Compared with the free molecule S(C7H7)2 (1), the bi-
dentate sulfane ligand in 4b,c has undergone only small
Z. Anorg. Allg. Chem. 2004, 630, 2438Ϫ2449
zaac.wiley-vch.de
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
2445

M. Herberhold, J. Liu, W. Milius, O. Tok, B. Wrackmeyer
Table 8 Angles /° in M(CO)4[S(C7H7)(η2-C7H7)] (M ϭ Mo (4b)
and W (4c))
stituent (C(1)ϪC(7)) is marginally more bent (cf. Fig. 7 and
Table 8). The axial conformation is required for π-com-
plexation via the C(4),C(5) double bond, which is length-
ened by 5Ϫ6 pm as a result of π-interaction with the metal
(C(4),C(5) 133.0(3) pm in 1, 138.8(15) and 138.6(8) pm in
4b and 4c, respectively). The distances SϪC(1) and SϪC(8)
and the angle C(1)ϪSϪC(8) are nearly unchanged if com-
pared with uncoordinated S(C7H7)2 (1) (SϪC(1) 184.43(18)
pm, C(1)ϪSϪC(8) 100.71(12)° [3]). The distance WϪS is
shorter in the tetracarbonyl 4c than in the (precursor)
pentacarbonyl 2c (252.85(11) versus 257.32(10) pm), but the
dihedral angles between the WϪS bond and the C(1)WC(8)
plane are very similar (147.5° in 2c, 150.8° in 4c).
M ϭ Mo (4b)
M ϭ W (4c)
C(4)-M-S
C(5)-M-S
C(4)-M-C(5)
84.8(3)
85.9(3)
32.3(4)
86.22(13)
84.63(13)
32.66(18)
C(4)-M-C(15)
C(4)-M-C(16)
C(4)-M-C(17)
C(4)-M-C(18)
C(5)-M-C(15)
C(5)-M-C(16)
C(5)-M-C(17)
C(5)-M-C(18)
C(15)-M-C(16)
C(15)-M-C(17)
C(15)-M-C(18)
C(16)-M-C(17)
C(16)-M-C(18)
C(17)-M-C(18)
C(15)-M-S
165.3(5)
78.4(4)
90.5(4)
109.5(4)
162.2(5)
110.6(4)
90.7(4)
77.2(4)
87.2(5)
91.2(5)
85.2(5)
85.0(4)
169.4(5)
87.9(4)
93.1(3)
93.1(3)
175.2(3)
94.6(3)
161.1(2)
76.8(2)
89.66(19)
111.4(2)
166.0(2)
109.4(2)
89.9(2)
78.9(2)
84.5(2)
92.3(2)
87.6(2)
Experimental
88.7(2)
169.5(2)
84.82(19)
92.80(17)
94.01(15)
174.43(16)
93.19(14)
The syntheses and all manipulations were routinely carried out un-
der argon; the solvents (THF, CH3CN, CH2Cl2) were dried and
saturated with argon. Standard procedures were used to prepare
the starting complexes, M(CO)6Ϫx(CH3CN)x (M ϭ Cr, Mo, W; x ϭ
1, 2, 3) [4,5], (norbornadiene)M(CO)4 (M ϭ Cr, Mo) [18] and
(mesitylene)Mo(CO)3 [55]. The ligand S(C7H7)2 (1) was obtained
[3] from tropylium bromide, C7H7Br [56], and H2S.
C(16)-M-S
C(17)-M-S
C(18)-M-S
C(1)-S-C(8)
C(1)-S-M
C(8)-S-M
99.6(5)
106.8(4)
109.1(3)
99.1(2)
107.86(16)
109.05(16)
Photo-induced decarbonylation of the hexacarbonyls M(CO)6 in
dilute THF solution to give the labile, solvent-stabilized pentacar-
bonyls, [M(CO)5](thf), was accomplished using the high-pressure
mercury arc Hanovia (700 W).
S-C(1)-C(2)
S-C(1)-C(7)
C(2)-C(1)-C(7)
C(1)-C(2)-C(3)
C(2)-C(3)-C(4)
C(3)-C(4)-C(5)
M-C(4)-C(5)
M-C(4)-C(3)
C(4)-C(5)-C(6)
M-C(5)-C(4)
107.4(7)
112.2(7)
113.4(9)
124.0(11)
127.8(12)
123.8(12)
73.2(6)
114.7(7)
127.5(11)
74.5(6)
112.6(3)
106.7(3)
112.1(4)
124.8(5)
127.1(5)
125.0(5)
74.1(3)
114.1(3)
125.1(5)
73.3(3)
Instrumentation: IR: Perkin Elmer 983 G (pentane). 1H and
13C NMR: Bruker ARX 250 (CDCl3, reference signal δ(1H) 7.24
(residual protons) and δ(13C) 77.0).
FD-MS: Varian, MAT 311A.
M-C(5)-C(6)
113.6(7)
126.5(11)
123.5(11)
111.1(8)
108.5(8)
109.7(9)
128.8(14)
125.9(14)
125.3(14)
126.9(15)
126.2(13)
125.9(11)
114.7(3)
127.9(5)
123.3(5)
112.3(4)
108.8(3)
111.0(4)
125.6(6)
125.9(6)
126.5(7)
126.3(7)
126.9(6)
125.3(5)
X-Ray crystallography: Siemens P4 (Mo-Kα radiation, λ ϭ 71.073
pm, graphite monochromator). Structure solution and refinement
with the program package SHELXTL-PLUS V.5.1. The crystallo-
graphic data and the structure refinement details are collected in
Table 9.
C(5)-C(6)-C(7)
C(1)-C(7)-C(6)
S-C(8)-C(9)
S-C(8)-C(14)
C(9)-C(8)-C(14)
C(8)-C(9)-C(10)
C(9)-C(10)-C(11)
C(10)-C(11)-C(12)
C(11)-C(12)-C(13)
C(12)-C(13)-C(14)
C(8)-C(14)-C(13)
Syntheses
Cr(CO)5[S(C7H7)2] (2a) and Mo(CO)5[S(C7H7)2] (2b)
A tetrahydrofuran (THF) solution (10 ml) containing 214 mg (1
mmol) S(C7H7)2 (1) was slowly added to an orange THF solution
(50 ml) which contained ca. 1 mmol M(CO)6Ϫx(CH3CN)x (x ϭ 1,
2, 3), previously prepared by refluxing 1 mmol M(CO)6 (M ϭ Cr
or Mo) in acetonitrile until 1.1 equivalents of CO had evolved. The
reaction mixture was stirred at room temperature overnight. Then
the solvent THF was removed under vacuum, the residue dissolved
in pentane and filtered through cellulose filter flocks. The pentane
filtrate was concentrated and cooled to Ϫ28 °C in a refrigerator,
where slow crystallization occured.
M-C(15)-O(1)
M-C(16)-O(2)
M-C(17)-O(3)
M-C(18)-O(4)
179.1(12)
173.7(12)
179.1(11)
174.7(11)
179.5(7)
174.5(5)
178.1(5)
174.0(5)
a)
Dihedral angles
α1
β1
α8
β8
45.6 (ax)
23.2
41.7 (ax)
22.8
46.1 (ax)
23.0
44.6 (ax)
21.8
C(1)SC(8)/MS
151.4
4.3
85.7
90
150.8
4.8
85.5
88.6
Cr(CO)5[S(C7H7)2], orange crystals, yield 155 mg (38.2 %), m.p.
C(4)MC(5)/MC(15,16,18)
O(1)C(15)MC(4,5)/MS
O(1)C(15)MC(4,5)/MC(17)O(3)
(dec.) above 77 °C, FD-MS: m/e 406 (Mϩ).
Mo(CO)5[S(C7H7)2], dark-yellow crystals, yield 175 mg (38.9 %),
m.p. (dec.) above 70 °C.
a) cf. Fig. 7. The numbering (α1, β1 and α8, β8) refers to the cyclohepta-2,4,6-
trienyl ring containing the carbon atoms C(1) or C(8), respectively.
W(CO)5[S(C7H7)2] (2c) and W(CO)5[S(CH2Ph)(C7H7)] (3c)
A solution of 352 mg (1 mmol) W(CO)6 in 100 ml of THF was
irradiated for 7 h with a high-pressure mercury arc (Hanovia,
700W), until the intense ν(CO) band of the educt (1974 cmϪ1) had
distortions. Both C7H7 ring substituents retain the axial
conformation as in 1, although the coordinated C7H7 sub-
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 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2004, 630, 2438Ϫ2449

Reactions of Di(1-cyclohepta-2,4,6-trienyl)sulfane, S(C7H7)2
Table 9 Crystallographic data and structure refinement details
W(CO)5[S(C7H7)2]
(2c)
Cr(CO)5[S(PhCH2)(C7H7)]
(3a)
M(CO)4[S(C7H7)(η2-C7H7)]
M ϭ Mo (4b)
M ϭ W (4c)
Empirical formula
C19H14WO5S
538.21
C19H14CrO5S
406.36
C18H14MoO4S
422.29
C18H14WO4S
510.20
Molecular mass / (g·moleϪ1
)
Temperature / K
Crystal system
Space group
296(2)
293(2)
monoclinic
C2/c
293(2)
monoclinic
P21/c
293(2)
monoclinic
P21/c
triclinic
¯
P1
Unit cell dimensions:
a / pm
b / pm
c / pm
920.49(16)
983.4(2)
1200.27(15)
69.868(13)
70.009(10)
89.151(15)
952.1(3)
2
1885.66(15)
1638.79(12)
1459.06(11)
90
121.061(5)
90
3862.3(5)
8
1.301
1602.0(2)
942.3(3)
1195.5(2)
90
102.011(9)
90
1765.2(6)
4
1596.44(19)
938.41(6)
1193.44(10)
90
102.316(7)
90
1746.8(3)
4
1.940
α / °
β / °
γ / °
Volume / (106 pm3)
Z
Density (calc.) / (Mg·mϪ3
)
1.877
1.589
0.879
Absorption coefficient / mmϪ1 6.201
0.716
6.750
F(000)
516
1552
848
976
Crystal dimensions / mm
Theta range / θ
Index ranges
0.22 ϫ 0.17 ϫ 0.12
1.94 to 25.00°
Ϫ10<h<1, Ϫ10<k<10,
Ϫ14<l<13
0.18 ϫ 0.15 ϫ 0.12
2.49 to 25.00°
Ϫ1<h<22, Ϫ1<k<19,
Ϫ17<l<15
3949
0.15 ϫ 0.14 ϫ 0.04
2.52 to 24.99°
Ϫ17<h<17, Ϫ1<k<11,
Ϫ1<l<12
0.25 ϫ 0.18 ϫ 0.10
2.53 to 25.00°
Ϫ18<h<18, Ϫ11<k<1,
Ϫ14<l<1
3987
Reflections collected
3609
3074
Independent reflections
Completeness to θ
Absorption correction
Max. and min. transmission
Refinement method
3043 [R(int) ϭ 0.0311]
91.0 %
Empirical
3342 [R(int) ϭ 0.0366]
98.6 %
Empirical
0.5917 and 0.5266
2314 [R(int) ϭ 0.0673]
74.6 %
Empirical
0.3507 and 0.2716
3056 [R(int) ϭ 0.0400]
99.5 %
Empirical
0.3379 and 0.2227
0.6969 and 0.4165
Full-matrix least-squares on F2 Full-matrix least-squares on F2 Full-matrix least-squares on F2 Full-matrix least-squares on F2
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I > 2σ (I)]
3043 / 0 / 236
1.079
R1 ϭ 0.0184,
wR2 ϭ 0.0468
R1 ϭ 0.0201,
wR2 ϭ 0.0478
0.0097(4)
3342 / 0 / 235
0.963
R1 ϭ 0.0594,
wR2 ϭ 0.1382
R1 ϭ 0.1187,
wR2 ϭ 0.1745
2314 / 0 / 217
0.998
R1 ϭ 0.0632,
wR2 ϭ 0.1296
R1 ϭ 0.1253,
wR2 ϭ 0.1587
3056 / 0 / 218
1.052
R1 ϭ 0.0251,
wR2 ϭ 0.0659
R1 ϭ 0.0293,
wR2 ϭ 0.0685
0.0029(2)
R indices (all data)
Extinction coefficient
Largest diff. peak and hole /
(10Ϫ6 e·pmϪ3
)
0.781 and -0.803
0.421 and -0.314
1.074 and -0.816
1.617 and -1.148
become weak. Then 214 mg (1 mmol) S(C7H7)2 (1) were added to
the yellow THF solution and the reaction mixture stirred for 1
day at room temperature. The orange-brown THF solution was
concentrated and purified by column chromatography on silica
(elution with pentane/THF (10:1)). The product 2c was obtained
as light-yellow crystals, m.p. 55 °C (beginning decomposition).
Yield 310 mg (57.6 %).
If the reaction mixture containing [W(CO)5](thf) and 1 is stirred
for 1 day at 40 °C (instead at room temperature) and worked up
in an analogous manner, the product is 3c. Yellow crystals, m.p.
(dec.) 55 °C. Yield 268 mg (49.8 %).
solvent was removed under vacuum, the residue dissolved in pen-
tane and the solution filtered over filter flocks. The filtrate was
concentrated and cooled to Ϫ28 °C. Yellow-green crystals, yield
165 mg (40.6 %).
c) A solution of 203 mg (0.5 mmol) 2a in 20 ml of THF was stirred
at 60 °C for 5 h, then concentrated to 1Ϫ2 ml and subjected by
column chromatography. Elution with pentane/THF (10:1) and
crystallization gave yellow-green 3a, yield 115 mg (56.7 %).
W(CO)5[S(CH2Ph)(C7H7)] (3c)
A solution of 269 mg (0.5 mmol) W(CO)5[S(C7H7)2] (2c) in 20 ml
of THF was kept at 50 °C for 5 h. The isomerized complex 3c was
isolated by concentrating the dark orange solution and chromato-
graphic purification. Yellow crystals, yield 142 mg (52.8 %).
Cr(CO)5[S(CH2Ph)(C7H7)] (3a)
a) The THF solution (100 ml) of 220 mg (1 mmol) Cr(CO)6 was
irradiated until the ν(CO) absorption in the IR spectra (1980 cmϪ1
)
Mo(CO)4[S(C7H7)(η2-C7H7)] (4b)
had almost disappeared (ca. 6 h). Then 214 mg (1 mmol) S(C7H7)2
(1) were added and the dark orange-red solution of [Cr(CO)5](thf)
was stirred at 25 °C for 2 days. The solvent THF was evaporated
and the concentrated solution (ca. 1Ϫ2 ml) given on top of a chro-
matography column containing silica in pentane. Elution with pen-
tane/THF (10:1) produced a solution from which yellow-green
crystals of 3a were obtained after concentration and cooling to
Ϫ28 °C. M.p. 65 °C (beginning decomposition). Yield 187 mg (46.1
%). FD-MS: m/e 406 (Mϩ).
a) A solution of 264 mg (1 mmol) Mo(CO)6 in 100 ml of THF was
irradiated with the UV lamp, until the strong ν(CO) band (1980
cmϪ1) had nearly disappeared (3Ϫ5 h), and then stirred in the pres-
ence of 214 mg (1 mmol) S(C7H7)2 (1) for 20 h at 25 °C. The solvent
THF was removed under high vacuum, the residue dissolved in
diethyl ether and the solution filtered over filter flocks. The filtrate
was concentrated and cooled to Ϫ28 °C. Yellow crystals of 4b were
slowly formed, m.p. 80 °C (beginning decomp.), total decomp. at
95 °C. Yield 146 mg (34.6 %). FD-MS: m/e 424 (Mϩ).
b) 214 mg (1 mmol) S(C7H7)2 (1) were added to the solution of
256 mg (1 mmol) Cr(CO)4(η4-nor-C7H8) in 30 ml of THF, and the
reaction solution stirred for 2 days at ambient temperature. The
b) A THF solution (30 ml) containing both 300 mg (1 mmol)
Mo(CO)4(η4-nor-C7H8) and 214 mg (1 mmol) S(C7H7)2 (1) was
Z. Anorg. Allg. Chem. 2004, 630, 2438Ϫ2449
zaac.wiley-vch.de
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
2447

M. Herberhold, J. Liu, W. Milius, O. Tok, B. Wrackmeyer
stirred for 2 days at room temperature. Then the solvent was evapo-
rated (together with nor-C7H8) under high vacuum and the residue
dissolved in diethyl ether. Filtration over cellulose filter flocks and
subsequent concentration to 1Ϫ2 ml gave a clear yellow solution
from which yellow crystals were formed over night at -28 °C. Yield
175 mg (41.3 %).
[2] M. Herberhold, J. Liu, W. Milius, Z. Anorg. Allg. Chem. 2004,
630, 1163.
[3] M. Herberhold, W. Milius, J. Liu, Z. Naturforsch. 2004, 60b,
673.
[4] B. L. Ross, J. G. Grasselli, W. M. Ritchey, H. D. Kaesz, Inorg.
Chem. 1963, 2, 1023.
[5] cf. W. A. Herrmann, Editor, in Herrmann/Brauer, Synthetic
Methods of Organometallic and Inorganic Chemistry, Vol. 1 (W.
A. Herrmann, A. Salzer, Literature, Laboratory Techniques
and Common Starting Materials); Georg Thieme Verlag,
Stuttgart-New York, 1996, p. 120.
W(CO)4[S(C7H7)(η2-C7H7)] (4c)
A THF solution (10 ml) containing 214 mg (1 mmol) S(C7H7)2
(1) was slowly added to an orange-red THF solution (50 ml) of
W(CO)6Ϫx(CH3CN)x (x ϭ 1, 2, 3). The combined solution was
stirred for 1 day. The dark-brown mixture was concentrated to 1Ϫ2
ml and then separated by column chromatography over silica (in
pentane). An orange zone was eluted using pentane/THF (10:1),
from which yellow-orange crystals could be obtained, m.p. 105 °C
(decomp. 105Ϫ112 °C). Yield 215 mg (42.2 %). FD-MS: m/e 510
(Mϩ).
[6] J. Sandström, Dynamic NMR Spectroscopy, Academic Press,
New York, 1982, p. 96.
ˇ
[7] E. W. Abel, K. G. Orrell, H. Rahoo, V. Sik, J. Organomet.
Chem. 1992, 441, 255.
[8] E. W. Abel, K. G. Orrell, K. B. Qureshi, V. Sik, Polyhedron
ˇ
1990, 9, 703.
Mo(CO)3[(η6-C7H7)-C7H7] (5b)
ˇ
[9] E. W. Abel, D. E. Budgen, I. Moss, K. G. Orrell, V. Sik, J.
An equimolar mixture of Mo(CO)6 (264 mg, 1 mmol) and S(C7H7)2
(1) (214 mg, 1 mmol) in 50 ml of THF was heated under reflux for
1 day. The solvent THF was evaporated and replaced by diethyl
ether, Et2O. The etheral solution was concentrated to 2 ml and
chromatographed over silica. Elution with pentane/THF (10:1) and
crystallization gave a mixture of orange crystals, m.p. 131 °C (cf.
117Ϫ119 °C [7]). FD-MS: m/e 364 (Mϩ); IR (pentane): ν(CO)
Organomet. Chem. 1989, 362, 105.
[10] E. W. Abel, I. Moss, K. G. Orrell, V. Sik, J. Organomet. Chem.
ˇ
1987, 326, 187.
ˇ
[11] E. W. Abel, S. K. Bhargava, P. K. Mittal, K. G. Orrell, V. Sik,
J. Chem. Soc. Dalton Trans. 1985, 1561.
[12] V. I. Minkin, I. E. Mikhailov, G. A. Dushenko, A. Zschunke,
Russ. Chem. Rev. 2003, 72, 867.
[13] B. E. Mann, Chem. Soc. Rev. 1986, 15, 167.
[14] J. J. Gajewski, Acc. Chem. Res. 1980, 13, 142.
[15] J. Jeener, B. H. Meier, P. Bachmann, R. R. Ernst, J. Chem.
Phys. 1979, 71, 4546.
[16] C. L. Perrin, T. J. Dwyer, Chem. Rev. 1990, 90, 935.
[17] G. A. Dushenko, I. E. Mikhailov, A. Zschunke, N. Hakam, C.
Mügge, V. I. Minkin, Mendeleev Commun. 1997, 50; see also
A. W. Zwaard, C. Erkelens, H. Kloosterziel, Recueil 1983,
102, 285.
[18] W. A. Herrmann, Editor, in Herrmann/Brauer, Synthetic
Methods of Organometallic and Inorganic Chemistry, Vol. 7 (W.
A. Herrmann, Transition metals Part 1); Georg Thieme Ver-
lag, Stuttgart-New York, 1997, p. 223.
1997(s), 1934(s), 1910(s) cmϪ1
.
Separation by TLC gave 85 mg (23.4 %) 5b-endo and 37 mg (10.2
%) 5b-exo.
5b-endo: 1H NMR (CDCl3): free ring: δ(H) ϭ 0.79m (H1, endo),
5.04m (H2, H7), 6.11m (H3, H6), 6.53t (H4, H5); coordinated ring:
δ(H’) ϭ 3.27m (H1’, endo), 3.98t (H2’, H7’), 4.92m (H3’, H6’), 5.92m
(H4’, H5’).Ϫ13C NMR (CDCl3): free ring: δ(C) ϭ 49.1 (C1), 122.4
(C2, C7), 126.3 (C3, C6), 130.7 (C4, C5); coordinated ring: δ(C’) ϭ
39.9 (C1’), 68.1 (C2’, C7’), 100.7 (C3’, C6’), 97.0 (C4’, C5’).
5b-exo: 1H NMR (CDCl3): free ring: δ(H) ϭ 2.07m (H1, exo),
5.16m (H2, H7), 6.25m (H3, H6), 6.70t (H4, H5); coordinated ring:
δ(H’) ϭ 2.42m (H1’, exo), 3.41t (H2’, H7’), 4.97m (H3’, H6’), 6.01m
(H4’, H5’).Ϫ13C NMR (CDCl3): free ring: δ(C) ϭ 43.0 (C1), 123.3
(C2, C7), 126.2 (C3, C6), 131.2 (C4, C5); coordinated ring: δ(C’) ϭ
39.4 (C1’), 62.6 (C2’, C7’), 100.3 (C3’, C6’), 97.4 (C4’, C5’).
[19] M. Herberhold, K. Bauer, W. Milius, Z. Naturforsch. 1999,
54b, 63.
[20] H. Adams, N. A. Bailey, D. G. Willett, M. J. Winter, J. Or-
ganomet. Chem. 1987, 333, 61.
[21] E. W. Abel, M. A. Bennett, R. Burton, G. Wilkinson, J. Chem.
Soc. 1958, 4559.
[22] C. Burschka, F.-E. Baumann, W. A. Schenk, Z. Anorg. Allg.
Chem. 1983, 502,191.
[23] A. L. Spek, Cryst. Struct. Commun. 1977, 6, 829.
[24] B. A. Karcher, R. A. Jacobsen, J. Organomet. Chem. 1977,
137, 387.
[25] J. C. Barnes, W. Bell, C. Glidewell, R. A. Howie, J. Organomet.
Chem. 1990, 385, 369.
[26] C. Bianchini, C. A. Ghilardi, A. Meli, S. Midollini, A. Orland-
ini, Organometallics 1982, 1, 778.
Crystal structure analyses
All non-hydrogen atoms were refined with anisotropic displace-
ment parameters. The hydrogen atoms are in calculated positions.
All hydrogen atoms were refined applying the riding model with
fixed isotropic temperature factors. Crystallographic data (exclud-
ing structure factors) for the structures described in the present
paper have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publications, no. CCDC-241940
(2c), CCDC-241938 (3a), CCDC-248937 (4b) and CCDC-241939
(4c). Copies of the data can be obtained on application to CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (fax: int. Codeϩ(1223)
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