Thiocarbene and alkoxycarbene tungsten complexes exhibit typically different reaction paths

Article abstract of DOI:10.1016/j.jorganchem.2007.03.014

The condensation of (butyl)thiocarbene tungsten complex [(OC)₅W{double bond, long}C(SEt)Bu] (1a) with an α,β-unsaturated secondary acid amide R²CH{double bond, long}CHC({double bond, long}O)NHR¹ 4 in the presence of POCl₃/Et₃N gives cyclopentadienimines 12, whereas the isostructural alkoxycarbene complex [(OC)₅W{double bond, long}C(OEt)Bu] (1c) under similar conditions affords a (N-enamino)ethoxycarbene compound 9. Furthermore, condensation of the (methyl)thiocarbene tungsten complex [(OC)₅W{double bond, long}C(SEt)Me] (1b) with an amide 4 yields cyclopentenimines 19 and allenylidene complexes 20, whereas the corresponding ethoxycarbene complex [(OC)₅W{double bond, long}C(OEt)CH₃] (1d) forms 4-NH-amino-1-tungsta-1,3,5-hexatrienes 16 under similar conditions.

Full text of DOI:10.1016/j.jorganchem.2007.03.014

Journal of Organometallic Chemistry 692 (2007) 2971–2989
www.elsevier.com/locate/jorganchem
Thiocarbene and alkoxycarbene tungsten complexes
q
exhibit typically different reaction paths
1
*
Frank Nitsche, Rudolf Aumann , Roland Fro¨hlich
Organisch-Chemisches Institut der Universita¨t Mu¨nster, Corrensstrasse 40, 48149 Mu¨nster, Germany
Received 16 January 2007; received in revised form 28 February 2007; accepted 8 March 2007
Available online 18 March 2007
Abstract
The condensation of (butyl)thiocarbene tungsten complex [(OC)5W@C(SEt)Bu] (1a) with an a,b-unsaturated secondary acid amide
R2CH@CHC(@O)NHR1 4 in the presence of POCl3/Et3N gives cyclopentadienimines 12, whereas the isostructural alkoxycarbene com-
plex [(OC)5W@C(OEt)Bu] (1c) under similar conditions affords a (N-enamino)ethoxycarbene compound 9. Furthermore, condensation
of the (methyl)thiocarbene tungsten complex [(OC)5W@C(SEt)Me] (1b) with an amide 4 yields cyclopentenimines 19 and allenylidene
complexes 20, whereas the corresponding ethoxycarbene complex [(OC)5W@C(OEt)CH3] (1d) forms 4-NH-amino-1-tungsta-1,3,5-hex-
atrienes 16 under similar conditions.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Thiocarbene complexes; Tungsten; Cyclopentadienes; Cyclopentenes
1. Introduction
base-induced conversion to allenes [10], a transformation
that could not be induced with isostructural (alkenyl)eth-
oxycarbene compounds, our attention was focused more
closely to reactivity differences between thiocarbene and alk-
oxycarbene complexes [11].
Fischer alkoxycarbene [1] and aminocarbene [2] com-
plexes have found wide application in organic synthesis [3],
whereas thiocarbene complexes have gained much less atten-
tion [4–7]. The reaction patterns of thiocarbene complexes
known so far are different from those of aminocarbene com-
plexes, but closely related to those of alkoxycarbene com-
pounds in so far as, for example, addition of isocyanides to
both thiocarbene and alkoxycarbene complexes gives keteni-
mine complexes and metal-free ketenimines [4b,8a], addition
of phosphines affords ylides [8b], addition of aminoalkynes
[4d,9] to (aryl)thiocarbene complexes produces (alke-
nyl)aminocarbene complexes and indenes [9], and addition
of terminal alkynes to (aryl)thiocarbene complexes affords
naphthalenes [4d]. Alerted by the observation that (alke-
nyl)thiocarbene complexes [4d] unexpectedly underwent a
2. Results and discussion
Fischer (alkyl)ethoxycarbene are well known to undergo
condensation reactions with aldehydes [12a,12b], ketones
[13], acid chlorides [12a,14], imines [15], aminoacetales
[16], and acid amides [17]. We now report on striking differ-
ences in condensation reactions of isostructural thiocar-
bene and ethoxycarbene complexes with a,b-unsaturated
secondary acid amides 4.
2.1. Condensation of thiocarbene complex 1a with
a,b-unsaturated secondary acid amides 4a–e
q
Organic syntheses via transition metal complexes, Part 121. For Part
To a mixture of thiocarbene complex 1a and an imidoyl
chloride 5a–e, generated in situ from an a,b-unsaturated
secondary acid amides 4a–e and POCl3/Et3N at ambient
temperature, was added triethylamine at ꢀ40 ꢁC to give a
120: see Ref. [19].
*
Corresponding author.
E-mail address: aumannr@uni-muenster.de (R. Aumann).
Crystal structure analysis.
1
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.03.014

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F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
cyclopentadienimine complex 12a–e, which could be iso-
lated by chromatography on silica gel.
1–3
a
b
c
d
X
R
S
n-Pr
S
H
O
n-Pr
O
H
Whereas base-induced condensation reactions of eth-
oxycarbene complexes 1c,d are readily performed at ambi-
ent temperature, thiocarbene complexes 1a,b would
rearrange under such conditions to vinyl thioethers
2a,b and 3a,b (Eq. (1)) rather than form a condensation
product. In order to obtain reasonable yields of condensa-
tion products from a thiocarbene complex and an imidoyl
chloride 5 (generated in situ from an acid amide 4 with
Based on the type of reaction products, the thiocarbene
complex 1a adds to secondary imidoyl chlorides 5 preferen-
tially in 1,2-fashion to give a b-iminocarbene complex 7
(Scheme 1). Products resulting from 1,4-addition were not
detected in this, but were found in related reactions with
a,b-unsaturated tertiary acid amides [18]. The reactivity pat-
terns of (b-imino)thiocarbene complexes 7 are typically dif-
ferent from those of (b-imino)ethoxycarbene complexes 6.
Whilst compounds 6 undergo a metalla(di-p-methane) rear-
rangement to (N-enamino)ethoxycarbene complexes 9,
[17d,19] the isostructural compounds 7 quite unexpectedly
afforded cyclopentadienimines 12 (Scheme 1). The forma-
tion of compounds 12 from complexes 7 is highly regio-
and stereoselective. According to experimental results and
theoretical calculations, alkoxycarbene complexes 6 seem
to prefer an associative reaction (involving a nucleo-philic
addition to the carbene carbon atom), whereas thiocarbene
complexes 7 preferentially undergo a dissociative reaction
1
POCl3/Et3N in ca. 48 h at 20 ꢁC according to H NMR
measurements) the reaction must be initiated under care-
fully controlled conditions by addition of triethylamine at
ꢀ40 ꢁC.
ðCOÞ5W ¼ CðXEtÞCH2R
1
NEt3ðcat:Þ
ðOCÞ W ðEtXÞCH ¼ CHR
ƒƒƒƒ!
5
2
þCO
ðEtXÞCH ¼ CHR
ð1Þ
ƒƒƒƒ!
ꢀWðCOÞ6
3
O
4
R2
[a]
NHR1
NR1
Cl
XEt
XEt
(OC)5W
NR1
(OC)5W
+ Et3N
+
(2)
[Et3NH]Cl
n
-Pr
R2
n-Pr
5
1a: X = S
1c: X = O
R2
6: X = O
7: X = S, R1 = CHR3R4
R2
(OC)5W
EtO
R1
Et
O
+
N
(OC)5W
[b]
(3)
(4)
6
N
n
-Pr
R1
n
-Pr
R2
R3
syn/anti-9
8
R2
R3
H
R4
R4
H
(OC)5W
-
EtSH
[c]
N
(OC)5W
N
+
R3
R4
7
N
n-Pr
n
-Pr
n-Pr
R2
R2
(OC)5W
10
12
11
4–14
R1
i-Pr
c-C6H11
CH(Et)Me Ph EtMe
i-Pr
c-C6H11 Me C5H10 34 31[d] 3[d]
R2 R3R4 12 13
14
13:14[e]
a
b
c
Ph
Me2
–
–
–
44
30
39
11
3
4:1
10:1
1.5:1
10:1
10:1
Ph C5H10
25
d
e
Me Me2 32 29[d] 3[d]
[a] POCl3/NEt3, 48 h, 20˚C; [b] metalla(di-π-methane)skeletal rearrangement; [c] π-cyclization;
[d] formed by base-induced rearrangement of compound 12; [e] product ratio according to
NMR measurements.
Scheme 1. (N-Enamino)ethoxycarbene complexes 9 and cyclopentadienimine complexes 12–14 by condensation of ethoxycarbene complex 1c and
thiocarbene complex 1a, respectively, with a,b-unsaturated secondary acid amides 4.

F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
2973
(by elimination of thiol to give vinylidene compounds 10)
[11]. It is suggested that cyclopentadienimines 12 are derived
from vinylidene compounds 10 in straight-forward reac-
tions by hydride transfer to give iminium carbonylmetalates
11, which undergo p-cyclization to compounds 12. Based on
a series of NMR analyses of product mixtures, it appears
that compounds 12 are generated as single isomers, which
rearrange during work-up to produce mixtures of com-
pounds 13 and 14 (Eq. (5)).
2.2. Condensation of (methyl)thiocarbene complex 1b with
a,b-unsaturated secondary acid amides 4
The condensation of the (methyl)thiocarbene complex
1b, and (methyl)ethoxycarbene complex 1d, respectively,
with an a,b-unsaturated secondary amide 4 takes a course
significantly different from that observed with the corre-
sponding (butyl)thiocarbene complex 1a, and (butyl)eth-
oxycarbene complex 1c, respectively (s. Scheme 1), except
for the first step, resulting in formation of a (b-imino)thio-
carbene complex 15, and (b-imino)ethoxycarbene complex
17, respectively (Scheme 2).
Ethoxycarbene complexes 15 form metallahexatrienes 16
which are stabilized by a hydrogen bridge [17d], whereas the
thiocarbene complexes 17 lack this type of stabilization and
therefore readily undergo p-cyclization to cyclopentenimine
complexes 19 (Eq. (9), Scheme 3), and – in competition – an
elimination of thiol to yield (deep blue) allenylidene com-
plexes 20 (Eq. (10), Scheme 3) [20]. The conformation
required for the p-cyclization of compounds 18 is readily
achieved due to the high flexibility of the carbon backbone
of this highly polar iminium carbonylmetalate.
R2
R2
R2
R3
R4
R3
R4
R3
R4
ð5Þ
N
N
n-Pr
n-Pr
N
n-Pr
(OC)5W
(OC)5W
(OC)5W
12
13
14
It should be noted that the intermediate 11 does not col-
lapse to form a pyrrole complex by an a-cyclization (Eq.
(6)), as it has been observed in related reactions of thiocar-
bene complexes with imidoyl chlorides [11], but is suffi-
ciently long-lasting to allow for rotation around the
central C–C bond (s. Scheme 1), as requisite for formation
of the p-cyclization product 12 in a thermodynamically
controlled process.
2.3. Structure elucidation
The molecular structures of the cyclopentadienes 12, 13
R3
1
R3 R4
and 14 are based on H and 13C NMR data. Compounds
R3 R4
R4
H
[a]
H
W(CO)5
-
12 can be distinguished from compounds 13 and 14 due to
the presence of two olefinic protons. The methylene unit
of the cyclopentadienes 13 and 14 exhibits an AB system
(13d: dH = 3.07 and 2.94, 2J = 22.7 Hz; 14d: dH = 3.42 and
2.76, 2J = 22.7 Hz). The A1-bands in the IR spectra of com-
-
H
+
N
(OC)5W
N
+
N
(OC)5W
-Pr
[a] π-cyclization
n-Pr
n
n-Pr
R2
R2
R2
11
pounds 12–14 (e.g. 13a: m = 2068.5 cmꢀ1) are in a range
ð6Þ
~
Et
Et
XEt
O
O
H
(OC)5W
(OC)5W
(OC)5W
N
R1
X = O
(OC)5W
N
R1
[a]
[a]
(7)
(8)
CH3
R2
1b,d
15
16
R2
R2
Cl
O
5
NR1
SEt
SEt
(OC)5W
+ POCl3/
NEt3
[Scheme 3]
H
N
R1
R2
N
X = S
R1
R2
R2
NHR1
4
17
18
4–18
a
b
D
f
g
h
i
j
K
R1
R2
i-Pr
Ph
quant.[c]
–
c-C6H11 i-Pr Me n-Pr Allyl Ph Me n-Pr
Ph
Me Ph
Ph
85[c]
56
Ph
Ph Me Me
[b]
[b]
[b]
[b]
[b]
[b]
[b]
5 [%]
18 [%][d]
36
21 49
–
–
–
–
[a] 1,3 H-shift; [b] NMR data were not recorded; [c] NMR data were recorded from 1:1 mixtures
of amides and POCl3 (yield estimated based on 1H NMR measurements); [d] isolated chemical
yield.
Scheme 2. 4-Amino-1-tungsta-1,3,5-hexatrienes 16 and 4-amino-1-tungsta-1,3,5-hexatrienes 18, respectively, by condensation of (methyl)ethoxycarbene
complexes 1d and (methyl)thiocarbene complexes 1b, respectively, with a,b-unsaturated secondary acid amides 4.

2974
F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
R2
R2
EtS
EtS
(9)
R1
SEt
N
C
N
W(CO)5
(OC)5W
a)
b)
R1
(
E
)-19
(Z
)-19
(OC)5W
H
N
R1
H
N
R1
R1
18
R2
N
+ 5
+
(10)
(OC)5W
C
- HCl
R2
SEt
path a) π-cyclization
path b) elimination
R2
20
21
18–21
R1
i-Pr
R2
Ph
19[a] (E/Z)-19 20[a]
21[a]
[c]
[c]
[c]
12
17
–
10
[e]
a
b
d
f
53
c-C6H11 Ph 36[b]
Me 21[b]
Ph 35
Ph 56[b]
–
i-Pr
Me
22
31
11
[d]
–
[e]
2:3
3:4
[e]
[e]
g
h
i
n-Pr
Allyl
Ph
Ph
Ph
22
2
7:10
[c]
37
–
j
Me
Me
Me
26
11
2:3
–
–
k
n-Pr
9:10
[a] isolated chemical yields; [b] corresponds to the yield of compound 18; [c] E/Z-19
equilibration not observed; [d] facile decomposition; [e] could not be isolated due to hydrolysis
on silica gel.
Scheme 3. Competition between the p-cyclization of 4-amino-1-tungsta-1,3,5-hexatrienes 18 to cyclopentenimines 19, and the elimination of ethanethiol to
allenylidene complexes 20.
expected for a W(CO)5 unit coordinated to the nitrogen of
an imino function [21]. The configurational assignment of
C12
the structures 13 and 14 is based on NOE experiments. Irra-
diation of the methylene protons of the cyclopentadiene 13a
results in a positive enhancement of the signal of the
CH2CH2CH3 protons. The high-field signal of the two
N(CH3)2 proton signals is observed on irradiation of the ole-
finic CH proton. Compound 14a shows the corresponding
NOEs between the CH2 group and the high-field signal of
the two N(CH3)2 proton signals as well as between the ole-
finic proton and the CH2CH2CH3 protons. This assignment
corresponds to chemical shifts observed for compounds 13c
and 14c. The (Z)-configuration is prevailing for steric rea-
sons and the low-field NCH3 proton signals can be assigned
to the (E)-isomers in which the methyl group is directed
towards the W(CO)5 unit.
C3
C11
C10
C6
C2
C4
C5
C7
C81
O25
C25
C24
N1
C82
C83
C9
C8
O24
W
C21
O21
C86
C84
C22
O22
C85
C23
O23
Fig. 1. Molecular structure of the cyclopentadienimine complex 13a with
selected bond lengths (A), bond angles (ꢁ) and dihedral angles (deg): W–
The cyclopentadienimine complex 13a was characterized
also by a crystal structure analysis (Fig. 1). The cyclopent-
adiene ring of compound 13a is almost planar [C9–C5–
C6–C7 0.5(3)ꢁ, C7–C8–C9–C5 –0.3(3)ꢁ]. The five-membered
ring and the plane comprised by the atoms W, N and C2 are
strongly distorted against each other [W–N1–C5–C6–
94.2(3)ꢁ, W–N1–C5–C9–82.8(3)ꢁ]. The C@N bond distance
˚
N1 2.286(2), N1–C2 1.289(4), N1–C5 1.446(4), C5–C6 1.340(4), C6–C7
1.511(4), C7–C8 1.495(4), C8–C9 1.361(4), C9–C5 1.460(4), C8–C81
1.465(4), C5–N1–C2 116.9(3), C5–N1–W 111.0(2), W–N1–C2 132.2(2),
N1–C2–C3 123.4(3), N1–C2–C4 121.2(3), C3–C2–C4 115.3(3), N1–C5–C9
122.2(3), N1–C5–C6 126.3(3), C6–C5–C9 111.5(3), C5–C6–C7 107.0(3),
C6–C7–C8 104.8(3), C7–C8–C9 108.3(3), C8–C9–C5 108.5 (3), W–N1–
C5–C6 94.2(3), W–N1–C5–C9 –82.8(3), C5–N1–C2–C4 178.4(3), C5–N1–
C2–C3 –2.9(4), C9–C5–C6–C7 0.5(3), C7–C8–C9–C5 –0.3(3), C7–C8–
C81–C82 –170.0(3).
˚
of 1.289(4) A in compound 13a is shorter than in the imin-
˚
ium carbonylmetalate 18b [C5–N1 1.328(3) A]. Compounds
18, 19 and 20 are easily distinguished by the position of the
A1-bands in the IR spectra: compounds 18 (e.g. 18f:
characteristical of r-coordination to C@NR group. The
very small A1-bands of the allenylidene complexes 20f–e
are shifted to exceptionally high wave numbers in a very nar-
m = 2060.9 cmꢀ1), characteristical of 1-tungsta-1,3,5-hex-
~
atrienes, compounds 19 (e.g. (Z)-19g: m = 2065.8 cmꢀ1),
~

F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
2975
different from that of an isostructural (b-imino)ethoxycar-
bene complex. Furthermore, fundamental changes in
reactivities are observed also within the groups of (b-
imino)heterocarbene complexes derived from methylcar-
bene, and alkylcarbene complexes other than methylcarbene
complexes, respectively. The condensation of (n-butyl)thio-
carbene complex [(OC)5W@C(SEt)(n-Bu)] (1a) with
a,b-unsaturated secondary acid amides 4 yields cyclopent-
adienimine complexes 12–14 (reaction initiated by 1,2-
addition and subsequent p-cyclization), whereas the
(methyl)thiocarbene complex [(OC)5W@C(SEt)CH3] (1b)
under similar conditions affords cyclopentenimine com-
plexes 19 and allenylidene complexes 20 (reaction initiated
by 1,2-addition and aubsequent hydrogen shift). The forma-
tion of different products from b-iminocarbene complexes is
attributed to minor differences in activation energies of the
single steps involved in the multistep-reaction sequences.
In line with theoretical predictions [11], the observation of
allenylidene complexes 20 indicates that a dissociative reac-
tion step is favoured with thiocarbene complexes over an
associative process.
C3
C2
O24
C24
S1
C1
C10
C9
C7
C4
C5
C11
O25
C25
C23
C6
O23
C8
W
C12
C21
C13
C22
O22
O21
N1
C14
C19
C18
C15
C16
C17
Fig. 2. Molecular structure of the 4-amino-1-tungsta-1,3,5-hexatriene 18b
with selected bond lengths (A), bond angles (ꢁ) and dihedral angles (ꢁ): W–
˚
C1 2.280(3), C1–C4 1.390(4), C4–C5 1.417(4), C5–C6 1.469(4), C6–C7
1.332(4), C7–C8 1.466(4), C5–N1 1.328(3), N1–C14 1.473(3), C1–S1
1.742(3), W–C1–S 106.7(1), S–C1–C4 116.2(2), W–C1–C4 137.0(2), C1–
C4–C5 129.0(3), C4–C5–N1 122.8(2), C6–C5–N1 117.7(2), C4–C5–C6
119.5(2), C5–C6–C7 123.9 (3), C6–C7–C8 127.1(3), C5–N1–C14 128.6(2),
W–C1–C4–C5 3.6(4), S–C1–C4–C5 179.2(2), C1–C4–C5–N1 0.1(4), C1–
C4–C5–C6 –178.5(2), C4–C5–C6–C7 –26.4(4), C5–C6–C7–C8 179.3(3),
C6–C7–C8–C9 180.0(3), C4–C5–N1–C14 175.0(2), C5–N1–C14–C15
162.5(3).
4. Experimental
All operations were carried out under an atmosphere of
argon. All solvents were dried and distilled prior to use. All
1H and 13C NMR spectra were routinely recorded in
CDCl3 or C6D6 on a Bruker ARX 300 instrument. COSY,
HMQC, HMBC, TOCSY and NOE experiments were per-
formed on either a Bruker AMX 400, a Varian 500 Inova
or a Varian 600 unity plus instrument. The chemical shifts
are given in ppm with TMS (d = 0 ppm) and the residue
signal of CDCl3 and C6D6 (d = 77 and 128 ppm) as the
row range of 2082.8 to 2083.0 cmꢀ1 (e.g. 20f: m = 2083.0
~
cmꢀ1) [22]. The configuration of compounds (Z)-19 and
(E)-19 was assigned by NOE experiments of compounds
19f and 19j. While the (Z)-isomers showed NOE between
N-CH3 and the CH2 group of the cyclopentene ring, the
expected NOE of the (E)-isomer between N-CH3 and the
olefinic CH proton could also be observed (see Fig. 2).
The ligand backbone W–C1–C4–C5–N1 of compound
18b is essentially planar. Its bond angles W–C1–C4
(137.0(2)ꢁ), C1–C4–C5 (129.0(3)ꢁ), C4–C5–N1 (122.8(2)ꢁ)
and C5–N1–C14 (128.6(2)ꢁ) are above 120ꢁ. The NH pro-
ton is located between two neighbouring carbonyl carbon
atoms. This 4-amino-1,3,5-metallatriene shows a carbimin-
ium carbonylmetalate unit, which is characterized by a pat-
tern of alternating bond distances of the W–C@C–C@N+
1
internal standards for H and 13C NMR spectra. IR spec-
tra were measured on a Bruker Vector 22 FT-IR spectrom-
eter. EI and ESI mass spectra were obtained on a double-
focussing Sektorfeld-MS MAT8200 (Thermo-Finnigan-
MAT, Bremen) and QUATTRO LCZ (Waters-Micromass,
Manchester, UK) spectrometers. HRMS spectra were
determined on a MicroTof (Bruker Daltronics, Bremen)
instrument with loop injection; for mass calibration sodium
formate clusters were used. Elemental analyses were deter-
mined on an elementar vario EL III instrument. Analytical
TLC plates, Merck TLC aluminium sheets Silica gel 60
˚
˚
˚
backbone [W–C1 2.280(3) A, C1–C4 1.390(4) A, C4–C5
˚
1.417(4) A, C5–N1 1.328(3) A]. The W–C1–C4–C5 portion
[dihedral angle 3.6(4)ꢁ] and the C1–C4–C5–N1 portion
[dihedral angle 0.1(4)ꢁ] of the molecule both adopt a cis
configuration. The C4–C5–C6–C7 unit [dihedral angle
ꢀ26.4(4)ꢁ] exhibits a cisoidal arrangement.
F254, were viewed by UV light (254 nm) and stained by
iodine. Rf values refer to TLC tests. Merck Silica gel 60
F was used for column chromatography. Flash chromatog-
raphy was performed under an argon atmosphere. Com-
pound 1a was prepared according to the literature [11].
3. Conclusion
4.1. Pentacarbonyl[1-(ethylsulfanyl)eth-1-ylidene]tungsten
(1b)
The reactivity patterns of alkylcarbene complexes 1a–d
with a,b-unsaturated secondary acid amides R2CH@
CHC(@O)NHR1 4 in the presence of POCl3/Et3N have
been unravelled, and it has been shown that b-iminocarbene
complexes are key-intermediates in these reactions. The
reactivity of a (b-imino)thiocarbene complexes is significally
(The procedure given is an adjustment of the procedure
presented by Aumann and Schro¨der [4b] to the special
requirements of (alkyl)thiocarbene complexes of tungsten;
see Eq. (1)). To pentacarbonyl[1-(ethoxy)eth-1-ylidene]-

2976
F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
tungsten (1d, 7.92 g, 20.0 mmol) and sodiumcarbonate
(2.12 g, 20.0 mmol) in 150 mL dry methanol in a 250-mL
round bottom flask is added ethanethiol (1.4 mL,
22.1 mmol) at ꢀ40 ꢁC. The progress of the reaction can be
monitored by TLC or by IR measurements. On addition
of phosphoric acid (2.16 g, 22.0 mmol) after 3 h stirring at
ꢀ40 ꢁC the color of the solution turns from yellow to red.
After addition of 75 mL of water the red carbene complex
is extracted with n-pentane. Crystallization on dry ice yields
analytically pure compound 1b (7.00 g, 85%, Rf = 0.3 in n-
pentane) in a 10:1 Z/E-ratio.
2H; 3-H2), 1.47 {1.47} (m, 2H; 4-H2), 1.28 {1.29} (t,
3J(H,H) = 7.4 Hz {7.4 Hz}, 3H; SCH2CH3), 0.96 {0.94} (t,
3J(H,H) = 7.1 Hz {7.4 Hz}, 3H; 5-H3); 13C NMR
(100 MHz, CDCl3, 300 K): d 200.2 and 197.1 {200.4 and
197.2} [each Cq, 1:4, trans- and cis-CO; W(CO)5], 140.2
{142.6} (CH; C2), 124.3 {122.9} (CH; C1), 40.1 {39.6}
(CH2; SCH2), 31.0 {34.3} (CH2; C3), 22.0 {21.9} (CH2;
C4), 14.8 {14.3} (SCH2CH3), 13.6 {13.5} (CH3; C5); IR
(cyclohexane) [cmꢀ1 (%)]: m = 2074.0 (10), 1939.9 (100),
~
1928.7 (40) [m(C„O)]; IR (diffuse reflexion) [cmꢀ1 (%)]:
~
m = 2073.3 (10), 1890.0 (100) [m(C„O)], 1454.1 (5); MS
(70 eV): m/z for 184W (%): 454.0 (30) [M]+, 426.0 (10)
[M ꢀ CO]+, 370.0 (10) [M ꢀ 3CO]+, 341.0 (100); HRMS
(ESI) calcd for C12H14SO5WNa [M + Na]+: 476.9963;
found: 476.9948.
S
S
(E)-1b
(Z
)-1b
(OC)5W
(OC)5W
CH3
CH3
4.2.2. Data for (Z)-3a {(E)-3a}
1H NMR (400 MHz, CDCl3, 300 K): d 5.93 {5.92} (dt,
3J(H,H) = 9.4 Hz {15.1 Hz}, 4J(H,H) = 1.4 Hz {1.4 Hz},
1H; 1-H), 5.57 {5.63} (dt, 3J(H,H) = 9.4 Hz {15.1 Hz},
3J(H,H) = 7.2 Hz {7.0 Hz}, 1H; 2-H), 2.66 {2.65} (q,
3J(H,H) = 7.4 Hz {7.4 Hz}, 2H; SCH2), 2.09 {2.06} (m,
2H; 3-H2), 1.41 {1.41} (m, 2H; 4-H2), 1.28 {1.27} (t,
3J(H,H) = 7.4 Hz {7.4 Hz}, 3H; SCH2CH3), 0.91 {0.91}
(t, 3J(H,H) = 7.4 Hz {7.4 Hz}, 3H; 5-H3); 13C NMR
(100 MHz, CDCl3, 300 K): d 129.4 {130.8} (CH; C2),
124.5 {122.4} (CH; C1), 31.0 {35.1} (CH2; C3), 27.6
{26.6} (CH2; SCH2), 22.0 {22.3} (CH2; C4), 15.3 {14.4}
(SCH2CH3), 13.5 {13.3} (CH3; C5).
4.1.1. Data for (Z)-1b {(E)-1b, ca. 10%}
1H NMR (300 MHz, CDCl3, 298 K): d 3.37 {3.43} (s,
3H; CCH3), 3.02 {3.64} (q, 3J(H,H) = 7.5 Hz {7.5 Hz},
2H; SCH2CH3), 1.37 {1.54} (t, 3J(H,H) = 7.5 Hz
{7.5 Hz}, 3H; SCH2CH3); 13C NMR (75 MHz, CDCl3,
298 K): d 332.2 {[23]} (Cq; W@C), 207.3 and 197.6 {[23]}
[each Cq, 1:4, trans- and cis-CO; W(CO)5], 47.7 {51.8}
(CH3; CCH3), 37.2 {42.4} (CH2; SCH2CH3), 11.5 {12.4}
(CH3; SCH2CH3); IR (cyclohexane) [cmꢀ1 (%)]:
~
m = 2066.4 (40) {2058.9 (4)}, 2058.9 (2), 1950.0 (100)
[m(C„O)]; MS (70 eV): m/z for 184W (%): 412 (20) [M]+,
486 (10) [M ꢀ CO]+, 328 (35), 298 (35), 270 (100), 127
(50); elemental analysis (%) calcd for C9H8O5SW (412.1):
C, 26.23; H, 1.96; found: C, 26.05; H, 1.70%.
4.3. Pentacarbonyl[(ethylsulfanyl)ethene, S–W]tungsten
(0) (2b), (ethylsulfanyl)ethene (3b)
To pentacarbonyl[1-(ethylsulfanyl)eth-1-ylidene]tung-
sten(0) (1b, 103 mg, 0.25 mmol) in 1 mL of CH2Cl2 is
added triethylamine (10 mg, 0.1 mmol). After 4 h, 20 ꢁC
the solution turns from red to yellow. Evaporation of sol-
vent gives compound 2b (Rf = 0.3 in n-pentane, yellow oil)
as the only product, which is transformed into compound
3b by addition of one equivalent of pyridine.
4.2. Pentacarbonyl[1-(ethylsulfanyl)pent-1-ene, S-W]-
tungsten (2a), 1-(ethylsulfanyl)pent-1-ene (3a)
To pentacarbonyl[1-(ethylsulfanyl)but-1-ylidene]tung-
sten(0) (1a, 113 mg, 0.25 mmol) in 1 mL of CH2Cl2 is
added triethylamine (10 mg, 0.1 mmol). Within 15 min at
20 ꢁC the solution turned from dark red to yellow. Solvent
was removed to give a 5:1 mixture of isomeric compounds
(Z)-2a and (E)-2a [Rf (1Z)-2a = 0.5, Rf (1E)-2a = 0.4 in n-
pentane, yellow oil], which are spontaneously transformed
into compounds 3a by addition of one equivalent of
pyridine.
(OC)5W
SEt
SEt
2b
3b
4.3.1. Data for 2b
1H NMR (400 MHz, C6D6, 300 K): d 5.47 (dd,
3
3J(H,H) = 16.3 Hz, J(H,H) = 9.3 Hz, 1H; 1-H), 4.91 (d,
(OC)5W
SEt
n-Pr
SEt
n-Pr
(E
/
Z)-2a
(E/Z)-3a
3
2J(H,H) = 0.8 Hz, J(H,H) = 16.3 Hz, 1 H; cis-2-H), 4.79
(d, 2J(H,H) = 0.8 Hz, 3J(H,H) = 9.3 Hz, 1H; trans-2-H),
2.06 (q, 3J(H,H) = 7.3 Hz, 2H; SCH2), 0.62 (t,
3J(H,H) = 7.3 Hz, 3H; SCH2CH3); 13C NMR (100 MHz,
CDCl3, 300 K): d 202.0 and 197.4 [each Cq, 1:4, trans-
and cis-CO; W(CO)5], 132.0 (CH; C1), 121.9 (CH; C2),
38.2 (CH2; SCH2), 13.9 (SCH2CH3); IR (cyclohexane)
4.2.1. Data for (Z)-2a{(E)-2a}
1H NMR (400 MHz, CDCl3, 300 K): d 5.97 {6.10} (dt,
3
3J(H,H) = 8.8 Hz {14.7 Hz}, J(H,H) = 7.4 Hz {7.1 Hz},
3
1H; 2-H), 5.88 {5.86} (dt, J(H,H) = 8.8 Hz {14.7 Hz},
4J(H,H) = 1.3 Hz {1.4 Hz}, 1H; 1-H), 2.84 {2.84} (q,
3J(H,H) = 7.4 Hz {7.4 Hz}, 2H; SCH2), 2.30 {2.21} (m,
[cmꢀ1 (%)]: m = 2075.1 (10), 1941.9 (100), 1930.9 (40)
~
[m(C„O)]; MS-ESI (ESI): m/z (%) = 411.1 (100) [M ꢀ H]ꢀ.

F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
2977
4.3.2. Data for 3b
1H NMR (400 MHz, C6D6, 300 K): d 6.17 (dd,
(10), 1969.4 (5), 1927.9 (100), 1913.1 (40) [m(C„O)]; HRMS
(ESI) calcd for C22H21NO5WNa [M + Na]+: 586.0825;
found: 586.0859; HRMS (ESI) calcd for C20H20NO3W [M
– 2CO ꢀ H]ꢀ: 506.0961; found: 506.0996; elemental analysis
(%) calcd for C22H21NO5W (563.1): C, 46.91; H, 3.76; N,
2.49; found: C, 46.98; H, 3.81; N, 2.36%.
3
3J(H,H) = 16.7 Hz, J(H,H) = 10.2 Hz, 1H; 1-H), 5.02 (d,
3J(H,H) = 10.2 Hz, 1H; cis-2-H), 4.98 (d, 3J(H,H) =
3
16.7 Hz, 1H; trans-2-H), 2.31 (q, J(H,H) = 7.4 Hz, 2H;
SCH2), 0.99 (t, 3J(H,H) = 7.4 Hz, 3H; SCH2CH3); 13C
NMR (100 MHz, CDCl3, 300 K): d 132.9 (CH; C1),
110.1 (CH; C2), 25.3 (CH2; SCH2), 14.1 (SCH2CH3).
4.4.2. Molecular structure analysis of bf 13a (code
3339.AUM)
Formula C22H21NO5W, Mr = 563.25 g molꢀ1, yellow
crystal, 0.25 · 0.20 · 0.10 mm, a = 10.061(1), b = 10.615(1),
4.4. Pentacarbonyl[isopropylidene-(4-phenyl-2-propyl-
cyclopenta-1,4-dienyl)-amine, N-W]tungsten(0) (13a),
pentacarbonyl[isopropylidene-(4-phenyl-2-propyl-
cyclopenta-1,3-dienyl)- amine, N-W]tungsten(0) (14a)
˚
c = 11.743(1) A, a = 71.60(1)ꢁ, b = 82.21(1)ꢁ, c = 68.48(1)ꢁ,
3
V = 1106.8(2) A , qcalcd = 1.690 g cmꢀ3, l = 52.49 cmꢀ1
,
˚
empirical absorption correction (0.354 6 T 6 0.622), Z =
(E)-N-Isopropyl-3-phenyl-acrylimidoyl chloride (5a)
(generated in situ by addition of (2E)-N-isopropyl-3-phenyl
acrylamide (4a, 378 mg, 2.0 mmol) to phosphorous oxy-
chloride (306 mg, 2.0 mmol) in dry dichloromethane
(2 mL) in a 3-mL screw-top vessel at 20 ꢁC, 48 h) was added
to pentacarbonyl[1-(ethylsulfanyl)but-1-ylidene]tungsten(0)
(1a, 454 mg, 1.0 mmol) in dry dichloromethane (3 mL). A
color change to dark blue is observed while triethylamine
(404 mg, 4.0 mmol) is added at ꢀ40 ꢁC. On warming to
20 ꢁC after 10 min, the color fades to yellow. Evaporation
of the solvent and flash chromatography at 20 ꢁC on silica
gel (40 · 1 cm, 10:1 n-pentane/diethyl ether) affords a bright
yellow 4:1 mixture of compounds 13a (260 mg, 46%,
Rf = 0.5 in 10:1 n-pentane/diethyl ether) and 14a (65 mg,
12%, Rf = 0.4 in 10:1 n-pentane/diethyl ether). A more polar
colorless fraction contained compound 21a (105 mg, 45%,
Rf = 0.3 in n-pentane/diethyl ether 10:1).
˚
ꢀ
2, triclinic, space group P1 (no. 2), k = 0.71073 A, T =
198 K, x and u scans, 7275 reflections collected ( h, k,
l), [(sinh)/k]max = 0.66 Aꢀ1, 5219 independent (Rint
=
˚
0.021) and 4869 observed reflections [I P 2r(I)], 265 refined
parameters, R = 0.023, wR2 ¼ 0:057, max./min. residual
electron density 0.71/–1.41 e Aꢀ3, hydrogen atoms calcu-
˚
lated and refined as riding atoms [24].
4.4.3. Data for 14a
1H NMR (400 MHz, CDCl3, 300 K): d 7.44 (m, 2H; o-
CH Ph), 7.33 (m, 2H; m-CH Ph), 7.20 (m, 1H; p-CH Ph),
6.73 (s, 1H; 3-H, NOE (+) with CH2CH2CH3), 3.89 and
2
3.28 (AB system, J(H,H) = 22.7 Hz, 2H; 5-H2, NOE (+)
with 60-NCH3 on irradiation at 3.28), 2.52 (s, 3H; 6-H3),
2.10 (m, 2H; CH2CH2CH3), 2.02 (s, 3H; 60-H3), 1.60 (m,
2 H; CH2CH2CH3), 0.99 (t, 3H; CH2CH2CH3); 13C
NMR (100 MHz, CDCl3, 300 K): d 202.4 and 198.4 [each
Cq, 1:4, trans- and cis-CO; W(CO)5], 184.8 (Cq; C@N),
151.8 (Cq; C1), 139.4 (Cq; C4), 135.1 (Cq; i-C Ph), 130.1
(Cq; C2), 128.7 (CH; m-CH Ph), 127.3 (CH; C3), 127.0
(CH; p-CH Ph), 124.6 (CH; o-CH Ph), 41.1 (CH2; C5),
32.0 (CH3; C6), 28.8 (CH2CH2CH3), 23.9 (CH3; C60),
20.9 (CH2CH2CH3), 14.5 (CH2CH2CH3).
Ph
Ph
4
4
5
5
3
3
6'
6
6'
6
2
2
13a
14a
1
1
N
N
(OC)5W
(OC)5W
4.5. Pentacarbonyl[cyclohexylidene-(4-phenyl-2-propyl-
cyclopenta-1,4-dienyl)-amine, N-W]tungsten(0) (13b),
pentacarbonyl[cyclohexylidene-(4-phenyl-2-propyl-
cyclopenta-1,3-dienyl)- amine, N-W]tungsten(0) (14b)
4.4.1. Spectroscopic data of 13a (obtained from a 4:1
mixture of compounds 13a and 14a)
1H NMR (300 MHz, CDCl3, 303 K): d 7.48 (m, 2H; o-
CH Ph), 7.33 (m, 2 H; m-CH Ph), 7.22 (m, 1H; p-CH Ph),
6.59 (s, 1H; 5-H, NOE (+) with 60-NCH3), 3.59 and 3.52
(E)-N-Cyclohexyl-3-phenyl-acrylimidoyl chloride (5b),
generated in situ from (2E)-N-cyclohexyl-3-phenyl acryl-
amide (4b, 458 mg, 2.0 mmol) and phosphorous oxychlo-
ride (306 mg, 2.0 mmol) in dry dichloromethane (2 mL)
at 20 ꢁC, 48 h in a 3-mL screw-top vessel, was added to
pentacarbonyl[1-(ethylsulfanyl)but-1-ylidene]tungsten(0)
(1a, 454 mg, 1.0 mmol) in dry dichloromethane (3 mL).
Triethylamine (404 mg, 4.0 mmol) was added at ꢀ40 ꢁC
and the mixture turned dark blue. The color faded to yel-
low on warming to 20 ꢁC after 10 min. Evaporation of
the solvent and flash chromatography at 20 ꢁC on silica
gel (40 · 1 cm, 10:1 n-pentane/diethyl ether) afforded a
bright yellow 10:1 mixture of compounds 13b (183 mg,
2
(AB system, J(H,H) = 23.0 Hz, 2H; 3-H2, NOE (+) with
CH2CH2CH3), 2.52 (s, 3H; 6-H3), 2.18 (m, 2H;
CH2CH2CH3), 2.02 (s, 3H; 60-H3), 1.60 (m, 2H;
CH2CH2CH3), 0.99 (t, 3H; CH2CH2CH3); 13C NMR
(75 MHz, CDCl3, 303 K): d 202.6 and 198.5 [each Cq, 1:4,
trans- and cis-CO; W(CO)5], 184.0 (Cq; C@N), 152.3 (Cq;
C1), 144.9 (Cq; C4), 135.4 (Cq; i-C Ph), 128.8 (CH; m-C
Ph), 127.3 (CH; p-C Ph), 126.5 (Cq; C2), 124.9 (CH; C5),
124.8 (CH; o-C Ph), 40.5 (CH2; C3), 31.9 (CH3; C6), 29.7
(CH2CH2CH3), 23.7 (CH3; C60), 22.0 (CH2CH2CH3), 14.7
(CH2CH2CH3); IR (cyclohexane) [cmꢀ1 (%)]: m = 2068.5
~

2978
F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
30%, Rf = 0.6 in 10:1 n-pentane/diethyl ether) and 14b
(18 mg, 3%, Rf = 0.5 in 10:1 n-pentane/diethyl ether).
(306 mg, 2.0 mmol) in dry dichloromethane (2 mL) at
20 ꢁC, 48 h in a 3-mL screw-top vessel, was added to pen-
tacarbonyl[1-(ethylsulfanyl)but-1-ylidene]tungsten(0) (1a,
454 mg, 1.0 mmol) in dry dichloromethane (3 mL). Trieth-
ylamine (404 mg, 4.0 mmol) was added to the mixture at
ꢀ40 ꢁC leading to a color change from red to dark blue.
On warming after 10 min to 20 ꢁC, the color faded to yel-
low. Evaporation of the solvent and flash chromatography
at 20 ꢁC on silica gel (40 · 1 cm, 10:1 n-pentane/diethyl
ether) afforded a bright yellow fraction of a 12:2:6:3 mix-
ture of compounds (Z)-13c, (E)-13c, (Z)-14c, (E)-14c
(370 mg, 64%, Rf = 0.4 in 50:1 n-pentane/diethyl ether).
Ph
Ph
4
4
5
3
3
5
6'
6
7'
7
6'
6
7'
7
2
2
13b
14b
1
1
N
8
N
8
(OC)5W
(OC)5W
4.5.1. Data for 13b
1H NMR (400 MHz, CDCl3, 300 K): d 7.48 (m, 2H; o-
CH Ph), 7.33 (m, 2H; m-CH Ph), 7.22 (m, 1H; p-CH Ph),
6.59 (s, 1H; 5-H), 3.55 (s, 2H; 3-H2), 2.89 (m, 2H; 6-H2),
2.37 (m, 2H; 60-H2), 1.93 and 1.67 (each m, 2:4 H; 7-, 70-
and 8-CH2), 2.18 (m, 2H; CH2CH2CH3), 1.55 (m, 2H;
CH2CH2CH3), 0.99 (t, 3H; CH2CH2CH3); 13C NMR
(100 MHz, CDCl3, 300 K): d 202.8 and 198.5 [each Cq,
1:4, trans- and cis-CO; W(CO)5], 189.6 (Cq; C@N), 151.4
(Cq; C1), 144.6 (Cq; C4), 135.4 (Cq; i-C Ph), 128.7 (CH;
m-C Ph), 127.2 (CH; p-C Ph), 126.6 (Cq; C2), 125.5 (CH;
C5), 124.8 (CH; o-C Ph), 42.1 (CH2; C6), 40.5 (CH2; C3),
33.0 (CH2; C60), 29.7 (CH2CH2CH3), 27.9 and 27.7
(CH2; C7 and C70), 25.1 (CH2; C8), 22.2 (CH2CH2CH3),
Ph
4
Ph
4
5
3
5
7'
6'
3
6'
2
2
1
1
N
N
6
6
(OC)5W
(OC)5W
7
(
Z
)-13c
(
E
)-13c
Ph
Ph
4
4
7'
6'
3
3
5
5
6'
14.6 (CH2CH2CH3); IR (cyclohexane) [cmꢀ1 (%)]: m =
2
2
~
1
1
N
N
2068.0 (10), 1968.5 (3), 1939.7 (25), 1928.2 (100), 1911.6
(40) [m(C„O)]; MS (70 eV): m/z for 184W (%): 603.3 (2)
[M]+, 547 (5) [M ꢀ 2CO]+, 279 (50) [M ꢀ W(CO)5]+, 250
(100) [M ꢀ W(CO)5 ꢀ C2H5]+; HRMS (ESI) calcd for
6
6
(OC)5W
)-14c
(OC)5W
)-14c
7
(Z
(E
C23H24NO3W
[M ꢀ 2CO ꢀ H]ꢀ:
546.1264;
found:
546.1292; elemental analysis (%) calcd for C25H25NO5W
(544.3): C 49.77, H 4.18, N 2.32; found C 49.83, H 4.22,
N 2.17.
Data for (E/Z)-13c and (E/Z)-14c (obtained from a
13:2:6:3 mixture of compounds (Z)-13c, (E)-13c, (Z)-14c,
(E)-14c; only some characteristic signals are given for
minor isomers).
4.5.2. Data for 14b
1H NMR (300 MHz, CDCl3, 303 K; for phenyl and
cyclohexyl signals see 13b): d 6.73 (s, 1H; 3-H), 4.01 and
4.6.1. Data for (Z)-13c
1H NMR (400 MHz, CDCl3, 300 K): d 7.48 (m, 2H; o-CH
Ph), 7.31 (m, 2 H; m-CH Ph), 7.20 (m, 1H; p-CH Ph), 6.57 (s,
1H; 5-H), 3.57 and 3.50 (AB system, 2J(H,H) = 22.8 Hz, 2H;
3-H2), 2.78(m, 2H; 6-H2), 2.16(m, 2H; CH2CH2CH3), 1.95(s,
2
3.18 (AB system, J(H,H) = 22.6 Hz, 2H; 5-H2), 0.88 (t,
3H; CH2CH2CH3); 13C NMR (75 MHz, CDCl3, 303 K):
d 202.6 and 198.4 [each Cq, 1:4, trans- and cis-CO;
W(CO)5], 190.6 (Cq; C@N), 150.9 (Cq; C1), 139.2 (Cq;
C4), 135.2 (Cq; i-C Ph), 130.2 (Cq; C2), 128.6 (CH; m-CH
Ph), 127.4 (CH; C3), 126.9 (CH; p-CH Ph), 124.5 (CH; o-
CH Ph), 42.3 (CH2; C6), 41.7 (CH2; C5), 33.3 (CH2;
C60), 28.8 (CH2CH2CH3), 27.9 and 27.7 (CH2; C7 and
C70), 25.8 (CH2; C8), 21.2 (CH2CH2CH3), 14.5
(CH2CH2CH3); for IR and MS data see compound 13b.
3
3H; 60-H3), 1.60 (m, 2H; CH2CH2CH3), 1.28 (t, J(H,H) =
7.5 Hz, 3H; 7-H3), 0.99 (t, 3J(H,H) = 7.4 Hz, 3H;
CH2CH2CH3); 13C NMR (100 MHz, CDCl3, 300 K): d
202.5 and 198.4 [each Cq, 1:4, trans- and cis-CO; W(CO)5],
188.3 (Cq; C@N), 152.4 (Cq; C1), 144.9 (Cq; C4), 135.3 (Cq;
i-C Ph), 128.6 (CH; m-C Ph), 127.1 (CH; p-C Ph), 126.3 (Cq;
C2), 124.8 (CH; C5), 124.7 (CH; o-C Ph), 40.4 (CH2; C3),
38.1 (CH2; C6), 29.5 (CH2CH2CH3), 22.0 (CH2CH2CH3),
20.3 (CH3; C60), 14.6 (CH2CH2CH3), 11.5 (CH3; C7); IR
4.6. Pentacarbonyl[(1-methyl-propylidene)-(4-phenyl-2-
propyl-cyclopenta-1,4- dienyl)-amine, N-W]tungsten(0)
(13c), pentacarbonyl[(1-methyl-propylidene)-(4-phenyl-2-
propyl-cyclopenta-1,3- dienyl)-amine, N-W]tungsten(0) (14c)
(cyclohexane) [cmꢀ1 (%)]: m = 2068.4 (10), 1969.4 (5), 1927.0
~
(100), 1912.4 (40) [m(C„O)]; HRMS (ESI) calcd for
C21H22NO3W [M ꢀ 2CO ꢀ H]ꢀ: 520.1107; found: 520.1124.
(E)-N-sec-Butyl-3-phenyl-acrylimidoyl chloride (5c),
generated from (2E)-N-sec-butyl-3-phenyl acrylamide (4c,
378 mg, 2.0 mmol) with phosphorous oxychloride
4.6.2. Data for (E)-13c
1H NMR (400 MHz, CDCl3, 300 K): d 6.56 (s, 1H; 5-H),
2.45 (s, 3H; 6-H3).

F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
2979
4.6.3. Data for (Z)-14c
1H NMR (400 MHz, CDCl3, 300 K): d 6.72 (s, 1H; 3-H),
3.96 and 3.27 (AB system, J(H,H) = 22.6 Hz, 2H; 5-H2),
1.93 (s, 3H; 60-H3).
(CH3; C60), 28.8 (CH2; CH2CH2CH3), 23.6 (CH3; C6),
20.7 (CH2; CH2CH2CH3), 14.2 (CH3; CH2CH2CH3), 14.0
2
(CH3; CHCH3); IR (cyclohexane) [cmꢀ1 (%)]: m = 2069.0
~
(10), 1969.4 (5), 1931.5 (100), 1927.1 (95), 1912.8 (40)
[m(C„O)]; MS (70 eV): m/z for 184W (%): 501 (24) [M]+,
473 (15) [M ꢀ CO]+, 445 (40) [M ꢀ 2CO]+; 415 (100).
4.6.4. Data for (E)-14c
1H NMR (400 MHz, CDCl3, 300 K): d 3.98 and 3.22
2
(AB system, J(H,H) = 22.6 Hz, 2H; 5-H2), 2.44 (s, 3H;
4.7.2. Data for 13d
1H NMR (400 MHz, CDCl3, 300 K): d 5.84 (s, br, 1H; 5-
6-H3).
2
H), 3.07 and 2.94 (AB system, J(H,H) = 22.7 Hz, 2H; 3-
4.7. Pentacarbonyl[isopropylidene-(3-methyl-5-propyl-
cyclopenta-1,4-dienyl)- amine, N-W]tungsten(0) (12d),
pentacarbonyl[isopropylidene-(4-methyl-2-propyl-
cyclopenta-1,4-dienyl)- amine, N-W]tungsten(0) (13d),
pentacarbonyl[isopropylidene-(4-methyl-2-propyl-
cyclopenta-1,3-dienyl)- amine, N-W]tungsten(0) (14d)
H2), 2.46 [s, 3H; 6-H3], 1.97 [s, 3H; 60-H3], 2.05 (m, 2H;
CH2CH2CH3), 2.03 (‘‘d’’, 3J(H,H) = 1.6 Hz, br, 3H;
3
CHCH3), 1.48 (m, 2H; CH2CH2CH3), 0.95 (t, J(H,H) =
7.3 Hz, 3H; CH2CH2CH3); 13C NMR (100 MHz, CDCl3,
300 K): d 202.9 and 198.5 [each Cq, 1:4, trans- and cis-CO;
W(CO)5], 183.3 (Cq; C@N), 151.6 (Cq; C1), 143.7 (Cq;
CCH3), 125.3 (CH; C5), 124.0 (Cq; C2), 44.0 (CH2; C3),
31.7 (CH3; C60), 29.5 (CH2; CH2CH2CH3), 23.5 (CH3;
C6), 22.0 (CH2; CH2CH2CH3), 16.3 (CH3; CHCH3), 14.6
(E)-N-Isopropyl-but-2-ene-1-carboximidoyl
chloride
(5d), generated from (E)-but-2-enonic acid isopropylamide
(4d, 254 mg, 2.0 mmol) with phosphorous oxychloride
(306 mg, 2.0 mmol) in dry dichloromethane (2 mL) at
20 ꢁC, 48 h in a 3-mL screw-top vessel, was added to pen-
tacarbonyl[1-(ethylsulfanyl)but-1-ylidene]tungsten(0) (1a,
454 mg, 1.0 mmol) in dry dichloromethane (3 mL). At
ꢀ40 ꢁC triethylamine (404 mg, 4.0 mmol) was added lead-
ing to a color change from red to dark blue. The color
faded to yellow on warming to 20 ꢁC after 10 min. Evapo-
ration of the solvent and flash chromatography at 20 ꢁC on
silica gel (40 · 1 cm, 10:1 n-pentane/diethyl ether) afforded
a bright yellow 6:10:1 mixture of compounds 12d, 13d and
14d (160 mg, 32%, Rf = 0.6 in 10:1 n-pentane/diethyl
ether). Compound 12d in CDCl3 is transformed completely
into a 10:1 mixture of compounds 13d and 14d in 24 h,
20 ꢁC.
(CH3; CH2CH2CH3); IR (cyclohexane) [cmꢀ1 (%)]: m =
~
2068.5 (10), 1969.0 (3), 1931.1 (100), 1926.4 (95), 1911.1
(40) [m(C„O)]; HRMS (ESI) calcd for C17H19NO5WNa
[M + Na]+: 524.0668; found: 524.0662; HRMS (ESI) calcd
for C15H19NO3W [M ꢀ 2CO ꢀ H]ꢀ: 444.0793; found:
444.0803.
4.7.3. Data for 14d
1H NMR (400 MHz, CDCl3, 300 K): d 5.94 (s, br, 1H;
2
3-H), 3.42 and 2.76 (AB system, J(H,H) = 22.7 Hz, 2H;
5-H2), 2.46 [s, 3H; 6-H3], 1.96 [s, 3H; 60-H3], for data of
CCH3 and n-propyl see 13d due to strong overlap; 13C
NMR (100 MHz, CDCl3, 300 K): d 202.8 and 198.4 [each
Cq, 1:4, trans- and cis-CO; W(CO)5], 184.2 (Cq; C@N),
150.3 (Cq; C1), 137.3 (Cq; CCH3), 129.0 (Cq; C2), 127.3
(CH; C3), 44.7 (CH2; C5), 32.0 (CH3; C60), 28.8 (CH2;
CH2CH2CH3), 23.7 (CH3; C6), 22.8 (CH2; CH2CH2CH3),
15.9 (CH3; CHCH3), 14.5 (CH3; CH2CH2CH3); for IR
and MS data see 13d.
3
4
4
2
4
5
3
5
3
6'
6
6'
6
6'
6
2
5
1
2
1
1
N
N
N
4.8. Pentacarbonyl[cyclohexylidene-(3-methyl-5-propyl-
cyclopenta-1,4-dienyl)- amine, N-W]tungsten(0) (12e),
pentacarbonyl[cyclohexylidene-(4-methyl-2-propyl-
cyclopenta-1,4-dienyl)- amine, N-W]tungsten(0) (13e),
pentacarbonyl[cyclohexylidene-(4-methyl-2-propyl-
cyclopenta-1,3-dienyl)- amine, N-W]tungsten(0) (14e)
(OC)5W
(OC)5W
(OC)5W
12d
13d
14d
Data for 12d, 13d and 14d (obtained from a 6:10:1 mix-
ture of compounds 12d, 13d and 14d).
(E)-N-Cyclohexyl-but-2-ene-1-carboximidoyl chloride
(5e), generated from (E)-but-2-enonic acid cyclohexylamide
(4e, 334 mg, 2.0 mmol) and phosphorous oxychloride
(306 mg, 2.0 mmol) as described above, was added to pen-
tacarbonyl[1-(ethylsulfanyl)but-1-ylidene]tungsten(0) (1a,
454 mg, 1.0 mmol) in dry dichloromethane (3 mL). Work-
up as described above afforded a bright yellow 10:1 mixture
of compounds 12e and 13e (186 mg, 34%, Rf = 0.7 in 10:1
n-pentane/diethyl ether). Compound 12e in CDCl3 is
slowly transformed into a 10:1 mixture of compounds
13e and 14e.
4.7.1. Data for 12d
1H NMR (400 MHz, CDCl3, 300 K): d 6.15 (m, 1H; 4-
H), 5.60 (m, 1H; 2-H), 3.21 (m, 1H; CHCH3), 2.50 (s,
3H; 6-H3), 1.94 (s, 3H; 60-H3), 2.12 and 1.81 (each m, each
1H; CH2CH2CH3), 1.62 (m, 2H; CH2CH2CH3), 1.19 (d,
3J(H,H) = 7.7 Hz, 3H; CHCH3), 0.99 (t, 3J(H,H) = 7.4 Hz,
3H; CH2CH2CH3); 13C NMR (100 MHz, CDCl3, 300 K): d
203.0 and 198.7 [each Cq, 1:4, trans- and cis-CO; W(CO)5],
183.8 (Cq; C@N), 156.9 (Cq; C1), 140.8 (Cq; C5), 136.1
(CH; C4), 121.2 (CH; C2), 44.1 (CH; CHCH3), 31.8

2980
F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
for C18H22NO3W [M ꢀ 2CO ꢀ H]ꢀ: 484.1106; found:
3
4
484.1120; elemental analysis (%) calcd for C20H23NO5W
(541.3): C, 44.38; H, 4.28; N, 2.59; found: C, 44.49; H,
4.18; N, 2.50%.
4
5
3
2
6'
6
6'
6
7'
7
7'
7
2
5
1
1
8
8
N
N
4.8.3. Data for 14e
1H NMR (400 MHz, CDCl3, 300 K): d 5.94 (s, br, 1H; 3-
(OC)5W
(OC)5W
2
H), 3.44 and 2.69 (AB system, J(H,H) = 22.6 Hz, 2H; 5-
12e
13e
H2), for data of CCH3, n-propyl and cyclohexyl see 13e
due to strong overlap; 13C NMR (100 MHz, CDCl3,
300 K): d 202.9 and 198.4 [each Cq, 1:4, trans- and cis-CO;
W(CO)5], 189.9 (Cq; C@N), 149.4 (Cq; C1), 137.6 (Cq;
CCH3), 129.1 (Cq; C2), 127.4 (CH; C3), 45.3 (CH2; C5),
42.3 (CH3; C60), 33.0 (CH3; C6), 28.8 (CH2; CH2CH2CH3),
27.7 and 27.0 (each CH2; C7 and C70), 25.0 (CH2; C8), 21.1
(CH2; CH2CH2CH3), 15.9 (CH3; CHCH3), 14.8 (CH3;
CH2CH2CH3); for IR and MS data see 13e.
4
5
3
6'
6'
2
1
N
8
6
7
(OC)5W
14e
Data for 12e, 13e and 14e (NMR and MS data of a
3:10:1 mixture of compounds 12e, 13e and 14e).
4.9. (E)-N-Isopropyl-3-phenyl-acrylimidoyl chloride (5a),
pentacarbonyl[(3-ethylsulfanyl-4-phenyl-cyclopent-2-
enylidene)-isopropyl- amine, N-W]tungsten(0) [(1 Z)-19a
and (1E)-19a], pentacarbonyl[3-(isopropylamino)-5-
phenyl-penta-1,2,4-triene-1- ylidene]tungsten(0) (20a),
(E)-N-isopropyl-3-phenyl-thioacrylimidic acid ethyl ester
(21a)
4.8.1. Data for 12e
1H NMR (400 MHz, CDCl3, 300 K): d 6.13 (m, 1H; 4-H),
5.61 (m, 1H; 2-H), 3.20 (m, 1H; CHCH3), 2.90 (m, 2H; 6-H2),
2.32 (m, 2H; 60-H2), 2.16 and 1.80 (each m, each 1H;
CH2CH2CH3), 1.61 (m, 2H; CH2CH2CH3), 1.19 (d,
3J(H,H) = 7.7 Hz, 3H; CHCH3), 0.99 (t, 3J(H,H) = 7.4 Hz,
3H; CH2CH2CH3); 13C NMR (100 MHz, CDCl3, 300 K): d
203.2 and 198.7 [each Cq, 1:4, trans- and cis-CO; W(CO)5],
189.2 (Cq; C@N), 155.9 (Cq; C1), 141.2 (Cq; C5), 135.7
(CH; C4), 122.2 (CH; C2), 44.0 (CH; CHCH3), 42.0 (CH2;
C6), 33.2 (CH3; C60), 28.8 (CH2; CH2CH2CH3), 27.7 and
27.5 (CH2; C7 and C70), 25.0 (CH2; C8), 20.8 (CH2;
CH2CH2CH3), 14.2 (CH3; CH2CH2CH3), 14.1 (CH3;
(E)-N-Isopropyl-3-phenyl-acrylimidoyl chloride (5a),
generated as described above from (2E)-N-isopropyl-3-phe-
nyl acrylamide (4a, 378 mg, 2.0 mmol) and phosphorous
oxychloride (306 mg, 2.0 mmol), was reacted with pentacar-
bonyl[1-(ethylsulfanyl)eth-1-ylidene]tungsten(0) (1b, 412
mg, 1.0 mmol). Work-up gave a colorless compound 21a
(23 mg, 10%, Rf = 0.5 in 10:1 n-pentane/diethyl ether) and
a thermolabile red compound (Rf = 0.4 in 10:1 n-pentane/
diethyl ether) which was transformed into compound (Z)-
19a (310 mg, 53%, Rf = 0.7 in 10:1 n-pentane/diethyl ether,
yellow oil) within 30 min. Equilibration of (Z)-19a and (E)-
19a (Rf = 0.5 in 10:1 n-pentane/diethyl ether) is accompa-
CHCH3); IR (cyclohexane) [cmꢀ1 (%)]: m = 2068.5 (10),
~
1968.7 (5), 1930.7 (100), 1926.6 (95), 1911.2 (40) [m(C„O)];
HRMS (ESI) calcd for C20H23NO5WNa [M + Na]+:
564.0981; found: 564.0972; HRMS (ESI) calcd for C18H22-
NO3W [M ꢀ 2CO ꢀ H]ꢀ: 484.1160; found: 484.1161.
1
nied by strong decomposition. H NMR data of (E)-19a
4.8.2. Data for 13e
1H NMR (400 MHz, CDCl3, 300 K): d 5.84 (s, br, 1H; 5-
were collected from a sample freshly chromatographed
and very dilute. A more polar dark red to violet fraction
contained compound 20a (64 mg, 12%, Rf = 0.5 in 1:1:1 n-
pentane/diethyl ether/dichloromethane, violet oil).
2
H), 3.07 and 2.95 (AB system, J(H,H) = 22.8 Hz, 2H; 3-
H2), 2.83 [m, 2H; 6-H2], 2.32 [s, 2H; 60-H2], 2.13 and 2.00
3
(m, 2H; CH2CH2CH3), 2.03 (‘‘d’’, J(H,H) = 1.5 Hz, br,
3H; CHCH3), 1.89 and 1.66 (each m, 2:4 H; 7-, 70- and 8-
CH2), 1.51 and 1.38 (each m, each 1H; CH2CH2CH3), 0.94
(t, 3J(H,H) = 7.3 Hz, 3H; CH2CH2CH3); 13C NMR
(100 MHz, CDCl3, 300 K): d 203.0 and 198.5 [each Cq, 1:4,
trans- and cis-CO; W(CO)5], 188.9 (Cq; C@N), 150.7 (Cq;
C1), 143.3 (Cq; CCH3), 126.0 (CH; C5), 124.2 (Cq; C2),
44.1 (CH2; C3), 42.0 (CH2; C6), 32.8 (CH2; C60), 29.5
(CH2; CH2CH2CH3), 27.8 and 27.6 (CH2; C7 and C70),
22.2 (CH2; CH2CH2CH3), 16.3 (CH3; CHCH3), 14.6 (CH3;
N
5a
Ph
Cl
4.9.1. Data for 5a (collected from a 1:1 mixture of amid and
phosphorous oxychloride in CDCl3 after completion of the
reaction at 20 ꢁC, 6 h)
1H NMR (400 MHz, CDCl3, 300 K): d 7.99 (d, 3J(H,H) =
15.2 Hz, 1H; PhCH), 7.77 (d, 3J(H,H) = 15.2 Hz, 1H;
PhCH@CH), 7.77 (m, 2H; o-CH Ph), 7.54 (m, 1H; p-CH
Ph), 7.46 (m, 2H; m-CH Ph), 4.54 (sept., 3J(H,H) = 6.6 Hz;
CH2CH2CH3); IR (cyclohexane) [cmꢀ1 (%)]: m = 2067.7
~
(10), 1968.2 (5), 1930.5 (100), 1925.8 (95), 1909.5 (40)
[m(C„O)]; HRMS (ESI) calcd for C20H23NO5WNa
[M + Na]+: 564.0981; found: 564.0977; HRMS (ESI) calcd

F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
2981
3
2H; NCH), 1.55 [d, J(H,H) = 6.6 Hz, 6H; NCH(CH3)2];
(Cq; W@C),[25] 151.6 (Cq; C4), 150.1 (CH; C6), 134.3
(Cq; i-C Ph), 131.2 (CH; p-CH Ph), 129.1 (CH; m-CH
Ph), 128.7 (CH; o-CH Ph), 121.8 (CH; C5), 112.2 (Cq;
C3), 50.3 (NCH), 21.7 (NCH(CH3)2); IR (dichlorometh-
13C NMR (100 MHz, CDCl3, 300 K): d 165.7 (Cq; C@N),
154.4 (CH; PhCH), 133.2 (CH; p-C Ph), 132.2 (Cq; i-C Ph),
129.9 (CH; o-C Ph), 129.1 (CH; m-C Ph), 117.3 (CH;
PhCH=CH), 53.5 (CH; NCH), 20.6 [NCH(CH3)2].
ane) [cmꢀ1 (%)]: m = 3365.9 (5) [m(N–H)], 2082.8 (1),
~
1993.7 (25), 1929.4 (100) [m(C„O)], 1625.9 (10), 1540.1
(10), 1467.1 (10), 1452.5 (10); HRMS (ESI) calcd for
C19H15NO5WNa [M + Na]+: 544.0355; found: 544.0340.
Ph
4
Ph
4
EtS
EtS
5
5
3
3
1
1
(Z )-19a
(E)-19a
2
2
SEt
N
W(CO)5
N
N
anti-21a
(OC)5W
SEt
4.9.2. Data for (Z)-19a{(E)-19a} (obtained from a 2:3 Z/E
mixture)
1H NMR (400 MHz, CDCl3, 300 K): d 7.36 {7.36} (m,
2H; m-CH Ph), 7.30 {7.30} (m, 1 H; p-CH Ph), 7.13
{7.13} (m, 2H; o-CH Ph), 6.89 {6.32} (d, 4J(H,H) = 1.4 Hz
{1.3 Hz}, 1H; 2-H), 4.08 {3.98} (m, 1H; 4-H), 3.82 {4.36}
(sept. {br}, 3J(H,H) = 6.6 Hz, 1H; NCH), 3.35 {3.45}
(dd, 2J(H,H) = 17.7 Hz {17.8 Hz}, 3J(H,H) = 7.6 Hz
N
syn-21a
4.9.4. Data for anti-21a{syn-21a} (obtained from a 1:1
mixture)
1H NMR (400 MHz, CDCl3, 300 K) d 7.47 {7.47} (each
m, 1H; p-CH Ph), 7.34 {7.34} (each m, 2H; m-CH Ph), 7.34
{7.34} (each m, 2H; o-CH Ph), 7.22 {7.27} (each d,
3J(H,H) = 16.2 Hz {15.8 Hz}, 1H; PhC-H), 6.99 {6.81}
[each d, 3J(H,H) = 16.2 Hz {15.8 Hz}, 1H; N@CC–H,
NOE (+) with NCH(CH3)2 {no NOE with NCH(CH3)2}],
4.11 {4.03} [each sept., 3J(H,H) = 6.2 Hz, 1H; NCH(CH3)2,
NOE (+) with N@CC–H {no NOE with N@CC–H}], 2.93
3
{7.5 Hz}, 1H; cis-5-H2), 2.96 {2.86} (q, J(H,H) = 7.5 Hz
{7.5 Hz},
2H;
SCH2CH3),
2.77
{2.99}
(dd,
2J(H,H) = 17.7 Hz {17.8 Hz}, J(H,H) = 2.6 Hz {2.4 Hz},
1H; trans-5-H2), 1.38 {1.32} (t, 3J(H,H) = 7.5 Hz, 3H;
SCH2CH3), 1.29 and 1.27 {1.41 and 1.40} [each d,
3J(H,H) = 6.6 Hz {6.6 Hz}, 3H; NCH(CH3)2]; 13C NMR
(100 MHz, CDCl3, 300 K): d 201.7 and 199.4 [Cq, 1:4,
trans- and cis-CO; W(CO)5], 182.5 (Cq; C@N), 172.5 (Cq;
C3), 141.0 (Cq; i-C Ph), 129.1 (CH; m-C Ph), 128.2 (CH;
C2), 127.8 (CH; p-C Ph), 127.1 (CH; o-C Ph), 60.4 (CH;
NCH), 52.1 (CH; C4), 41.9 (CH2; C5), 27.1 (SCH2CH3),
23.8 and 23.7 [NCH(CH3)2], 13.3 (SCH2CH3); IR (cyclo-
3
3
{2.96} (each q, J(H,H) = 7.4 Hz, 2H; SCH2), 1.29 {1.28}
(t, 3J(H,H) = 7.4 Hz, each 3H; SCH2CH3), 1.22 {1.17}
[each d, J(H,H) = 6.2 Hz, 6 H; NCH(CH3)2]; 13C NMR
3
(100 MHz, CDCl3, 300 K): d 158.0 {157.7} (Cq; C@N),
136.8 {136.7} (CH; Ph-CH), 136.7 {136.0} (Cq; i-C Ph),
129.0 {128.9} (CH; p-CH Ph), 128.6 {128.7} (CH; m-CH
Ph), 127.3 {127.3} (CH; o-CH Ph), 120.0 {126.5} (CH;
Ph-CH@CH), 53.8 {51.6} [NCH(CH3)2], 23.7 {27.0}
(SCH2), 24.1 {23.2} [NCH(CH3)2], 14.3 {15.7} (SCH2CH3).
hexane) [cmꢀ1 (%)]: m =2065.7 (30), 1962.4 (5), 1927.1
~
(100), 1918.3 (95), 1908.0 (95) [m(C„O)], 1569.7 (10),
1545.4 (10) [m(C@C) and m(C@N)]; IR (diffuse reflexion)
[cmꢀ1 (%)]: m = 2064.4 (10), 1965.8 (4), 1875.5 (100),
~
1568.3 (7), 1544.0 (15), 1494.5 (1), 1454.0 (3), 1304.5 (1),
1172.8 (1); HRMS (ESI) calcd for C21H21NSO5WNa
[M + Na]+: 606.0543; found: 606.0513.
IR (cyclohexane) [cmꢀ1 (%)]: m =1630.0 (50), 1587 (100)
~
[m(C@O)]; MS (70 eV): m/z for 184W (%): 233.1 (5) [M]+,
172.1 (35) [M ꢀ SEt]+, 130.0 (100) [M ꢀ SEt ꢀ C3H6]+;
HRMS (ESI) calcd for C14H19NS [M + H]+: 234.1313;
found: 234.1311.
H
N
•
•
(OC)5W
1
20a
4
5
6
2
3
4.10. (2s-cis, 3Z, 4s-cis,5E )-1,1,1,1,1-Pentacarbonyl-2-
ethylsulfanyl-6-phenyl-4-N-cyclohexylamino-1-tungsten-
1,3,5-hexatriene (18b), pentacarbonyl[(3-ethylsulfanyl-4-
phenyl-cyclopent-2-enylidene)- cyclohexyl-amine, N-
W]tungsten(0) [(1Z)-19b and (1E)-19b],
Ph
4.9.3. Data for 20a
1H NMR (400 MHz, CDCl3, 300 K): d 9.52 (s, br, 1H;
NH), 7.98 (d, 3J(H,H) = 15.3 Hz, 1H; PhCH), 7.53 (m,
2H; o-CH Ph), 7.34 (m, 1H; p-CH Ph), 7.31 (m, 2H; m-
CH Ph), 6.95 (m, 3J(H,H) = 15.3 Hz, 1H; PhCH@CH),
4.62 (m, 1H; NCH), 1.40 (d, 3J(H,H) = 6.6 Hz, 6H;
NCH(CH3)2); 13C NMR (100 MHz, CDCl3, 300 K): d
203.3 and 197.4 [Cq, 1:4, trans- and cis-CO; W(CO)5],
pentacarbonyl[3-(cyclohexylamino)-5-phenyl-penta-1,2,4-
triene-1-ylidene]tungsten(0) (20b)
(E)-N-Cyclohexyl-3-phenyl-acrylimidoyl chloride (5b),
generated from (2E)-N-cyclohexyl-3-phenyl acrylamide
(4b, 378 mg, 2.0 mmol) and phosphorous oxychloride
(306 mg, 2.0 mmol), was reacted with pentacarbonyl-

2982
F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
˚
[1-(ethylsulfanyl)eth-1-ylidene]tungsten(0) (1b, 412 mg, 1.0
mmol). Work-up afforded red crystals of compound 18b
(225 mg, 36%, Rf = 0.3 in 10:1 n-pentane/diethyl ether).
Compound 18b was transformed into (Z)-19b (Rf = 0.7 in
10:1 n-pentane/diethyl ether, yellow oil) in CDCl3, 20 ꢁC,
within 3 h. Equilibration of (Z)-19b and (E)-19b in solution
was accompanied by strong decomposition. A more polar
dark red to violet fraction yielded compound 20b (95 mg,
17%, Rf = 0.3 in n-pentane/dichloromethane 1:1, violet
oil).
density 1.22/ꢀ0.93 e Aꢀ3, hydrogen atom at N1 from differ-
ence fourier map, others calculated and refined as riding
atoms [24].
Ph
4
Ph
4
EtS
EtS
5
5
3
3
1
1
(Z)-19b
(E)-19b
2
2
N
W(CO)5
N
(OC)5W
SEt
1
2
(OC)5W
4.10.3. Data for (Z)-19b
3
H
N
1H NMR (400 MHz, CDCl3, 300 K): d 7.36 (m, 2H; m-
CH Ph), 7.30 (m, 1H; p-CH Ph), 7.13 (m, 2H; o-CH Ph),
6.91 (s, 1H; 2-H), 4.07 (m, 1H; Ph-CH), 3.34 (dd,
18b
4
6
5
Ph
3
2J(H,H) = 17.7 Hz, J(H,H) = 7.5 Hz, 1H; cis-5-H2), 2.95
(q, 3J(H,H) = 7.5 Hz, 2H; SCH2CH3), 3.30 (m, 1H;
NCH), 2.75 (dd, 2J(H,H) = 17.7 Hz, 3J(H,H) = 2.6 Hz,
1H; trans-5-H2), 1.87,1.66 and 1.29 (each m, 4:4:2H;
CH2-cyclohexyl), 1.37 (t, 3J(H,H) = 7.5 Hz, 3H;
SCH2CH3); 13C NMR (100 MHz, CDCl3, 300 K): d 201.8
and 199.5 [each Cq, 1:4, trans- and cis-CO; W(CO)5],
182.6 (Cq; C@N), 172.4 (Cq; C3), 140.9 (Cq; i-C Ph),
129.1 (CH; m-C Ph), 128.2 (CH; C2), 127.7 (CH; p-C
Ph), 127.1 (CH; o-C Ph), 69.1 (CH; NCH), 52.0 (CH;
C4), 41.9 (CH2; C5), 34.1 (br), 25.8, 25.2, 24.9 (each m,
2:2:1; CH2-cyclohexyl), 27.0 (SCH2CH3), 13.2 (SCH2CH3);
4.10.1. Spectroscopic data of 18b
1H NMR (600 MHz, CDCl3, 233 K): d 10.06 (d, br,
3J(H,H) = 8.1 Hz 1H; NH), 7.63 (m, 2H; o-CH Ph), 7.57
(dd, 3J(H,H) = 15.9 Hz, 3J(H,H) = 3.1 Hz, 1H; CH-Ph),
7.51 (m, 3H; m/p-CH Ph), 7.00 (d, 3J(H,H) = 15.9 Hz,
1H; CHCHPh), 6.86 (s, 1H; 3-H), 3.75 (m, 1H; NCH),
2.94 (q, 2H; SCH2CH3), 2.15, 1.90, 1.73, 1.65, 1.37 (each
m, 2:2:1:3:2H; CH2-cyclohexyl), 1.33 (t, 3H; SCH2CH3);
13C NMR (150 MHz, CDCl3, 233 K): d 225.4 (Cq;
W@C), 202.9 and 198.7 [Cq, 1:4, trans- and cis-CO;
W(CO)5], 160.4 (Cq; C4), 143.0 (CH; C6), 134.0 (Cq; i-C
Ph), 130.8 (CH; p-C Ph), 129.1 (CH; m-C Ph), 127.9
(CH; o-C Ph), 119.9 (CH; C5), 115.1 (CH; C3), 54.9
(CH; NCH), 32.5 (SCH2CH3), 32.1 (CH2; NCHCH2),
24.7 (NCHCH2CH2), 24.5 (NCHCH2CH2CH2), 11.4
IR (cyclohexane) [cmꢀ1 (%)]: m = 2065.2 (30), 1961.5 (5),
~
1927.9 (100), 1918.4 (95), 1915.3 (95), 1907.3 (100)
[m(C„O)], 1567.6 (10), 1545.7 (15) [m(C@C) and m(C@N)];
IR (diffuse reflexion) [cmꢀ1 (%)]: m = 2928.0 (5), 2857.0
~
(2), 2064.0 (10), 1965.0 (4), 1889.9 (100), 1567.5 (10),
1541.0 (20), 1453.2 (4); HRMS (ESI) calcd for
C24H25NSO5WNa [M + Na]+: 646.0856; found: 646.0859.
(SCH2CH3); IR (cyclohexane) [cmꢀ1 (%)]: m = 2060.6
~
(40), 1934.9 (100), 1918.4 (70), 1907.9 (40) [m(C„O)]; IR
(diffuse reflexion) [cmꢀ1 (%)]: m = 2056.6 (20), 1882.2
~
H
N
(100), 1627.7 (5), 1578.7 (5), 1505.5 (20), 1452.5 (3),
1387.9 (3), 1363.6 (4), 1325.6 (4), 1310.8 (5), 1288.1 (7),
1257.3 (4), 1233.6 (4); HRMS (ESI) calcd for
C24H25NSO5WNa [M + Na]+: 646.0857; found: 646.0842;
elemental analysis (%) calcd for C24H25NSO5W (623.4):
C, 46.24; H, 4.04; N, 2.25; found C, 46.15; H, 3.82; N,
2.18%.
•
•
20b
(OC)5W
1
3
4
5
6
2
Ph
4.10.4. Data for 20b
1H NMR (400 MHz, CDCl3, 300 K): d 9.24 (br, 1H;
3
NH), 7.99 (d, J(H,H) = 15.4 Hz, 1H; CH@CHPh), 7.45
4.10.2. Molecular structure analysis of 18b (code
3657.AUM)
(m, 2H; o-CH Ph), 7.31 (m, 3H; m-and p-CH Ph), 6.88
(d, 3J(H,H) = 15.4 Hz, 1H; CH=CHPh), 4.32 (m, 1H;
NCH), 2.18 and 1.41 (each m, 2H; NCHCH2), 1.82 and
1.42 (each m, 2H; NCHCH2CH2), 1.63 (m, 2H;
NCHCH2CH2CH2); 13C NMR (100 MHz, CDCl3,
300 K): d 203.4 and 197.4 [Cq, 1:4, trans- and cis-CO;
W(CO)5], 193.4 (Cq, small/broad; W@C), 151.2 (Cq; C4),
150.1 (CH; CH=CHPh), 134.2 (Cq; i-C Ph), 131.3 (CH;
p-CH Ph), 129.1 (CH; m-CH Ph), 128.6 (CH; o-CH Ph),
121.7 (CH; CH@CHPh), 112.3 (Cq, small/broad; C3),
57.3 (CH; NCH), 32.0 (CH2; NCHCH2), 25.1 (CH2;
Formula C24H25NO5SW, Mr = 623.36 g molꢀ1
,
red
crystal, 0.45 · 0.25 · 0.20 mm, a = 15.684(1), b = 8.513(1),
3
˚
˚
c = 18.472(1) A, b = 97.89(1)ꢁ, V = 2443.0(4) A , qcalcd
=
1.695 g cmꢀ3, l = 48.47 cmꢀ1, empirical absorption correc-
tion (0.219 6 T 6 0.444), Z = 4, monoclinic, space group
˚
P21/n (no. 14), k = 0.71073 A, T = 198 K, x and u scans,
15269 reflections collected ( h,
k,
l), [(sinh)/
k]max = 0.67 Aꢀ1, 5861 independent (Rint = 0.029) and
5106 observed reflections [I P 2r(I)], 295 refined parame-
ters, R = 0.023, wR2 ¼ 0:051, max./min. residual electron
˚

F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
2983
NCHCH2CH2CH2), 24.5 (CH2; NCHCH2CH2); IR
(ESI) calcd for C16H19NSO5W [M – H]ꢀ: 520.0410; found:
520.0415; elemental analysis (%) calcd for C16H19NSO5W
(521.2): C, 36.87; H, 3.67; N, 2.69; found C, 36.79; H,
3.69; N, 2.61%.
(dichloromethane) [cmꢀ1 (%)]: m = 3363.9 (5) [m(N–H)],
~
2082.8 (2), 1994.2 (30), 1929.1 (100) [m(C„O)], 1625.7
(10), 1539.1 (10); IR (diffuse reflexion) [cmꢀ1 (%)]:
~
m = 2082.6 (0.5), 1995.9 (10), 1898.1 (100) [m(C„O)];
HRMS (ESI) calcd for C22H19NO5WNa [M + Na]+:
Me
4
Me
4
584.0668; found: 584.0683.
EtS
EtS
5
5
3
3
1
1
(Z)-19d
(E)-19d
2
2
4.11. (2s-cis,3Z,4s-cis,5E)-1,1,1,1,1-Pentacarbonyl-2-
ethylsulfanyl-6-methyl-4-N-isopropylamino-1-tungsten-
1,3,5-hexatriene (18d), pentacarbonyl[(3-ethylsulfanyl-4-
methyl-cyclopent-2-enylidene)-isopropyl-amine, N-
W]tungsten(0) [(1Z)-19d]
N
W(CO)5
N
(OC)5W
4.11.2. Data for (Z)-19d
(E)-N-Isopropyl-but-2-ene-1-carboximidoyl
chloride
1H NMR (400 MHz, CDCl3, 300 K): d 6.66 (d,
3J(H,H) = 1.2 Hz, 1 H; 2-H), 3.83 (sept., 3J(H,H) = 6.6 Hz,
1H; NCH), 3.08 (dd, 2J(H,H) = 17.1 Hz, 3J(H,H) = 7.0 Hz,
(5d), generated as described above from (E)-but-2-enonic
acid isopropylamide (4d, 254 mg, 2.0 mmol) and phospho-
rous oxychloride (306 mg, 2.0 mmol) was reacted with pen-
tacarbonyl[1-(ethylsulfanyl)eth-1-ylidene]tungsten(0) (1b,
412 mg, 1.0 mmol). Addition of triethylamine (808 mg,
8.0 mmol) at ꢀ78 ꢁC and direct transfer of the mixture to
a precooled column at ꢀ78 ꢁC on silica gel (15 · 2 cm,
1:1 n-pentane/diethyl ether) afforded a red fraction, from
which red crystals of compound 18d were obtained at
ꢀ20 ꢁC from n-pentane (110 mg, 21%, Rf = 0.5 in 10:1 n-
pentane/diethyl ether). In solution (CDCl3, 20 ꢁC) 18d
was transformed into (Z)-19d (Rf = 0.6 in 10:1 n-pentane/
diethyl ether, yellow oil) within 3 h. Equilibration of (Z)-
19d and (E)-19d (Rf = 0.5 in 10:1 n-pentane/diethyl ether)
is accompanied by strong decomposition.
3
1H; cis-5-H2), 3.02 (m, 1H; CHCH3), 2.98 (q, J(H,H) =
7.4 Hz, 2H; SCH2CH3), 2.38 (dd, 2J(H,H) = 17.1 Hz,
3J(H,H) = 2.0 Hz, 1H; trans-5-H2), 1.43 (t, 3J(H,H) =
3
7.4 Hz, 3H; SCH2CH3), 1.28 and 1.27 [each d, J(H,H) =
3
6.6 Hz, 3H; NCH(CH3)2], 1.24 (d, J(H,H) = 7.0 Hz, 3H;
CHCH3); 13C NMR (100 MHz, CDCl3, 300 K): d 201.7
and 199.4 [each Cq, 1:4, trans- and cis-CO; W(CO)5], 182.5
(Cq; C@N), 174.6 (Cq; C3), 126.7 (CH; C2), 60.1 (CH;
NCH), 40.9 (CH; C4), 40.2 (CH2; C5), 26.9 (SCH2CH3),
23.8 and 23.7 (each CH3; NCH(CH3)2]), 20.6 (CH3;
CHCH3), 13.4 (SCH2CH3); IR (cyclohexane) [cmꢀ1 (%)]:
~
m = 2065.2 (25), 1928.9 (70), 1922.5 (60), 1915.4 (55),
1908.3 (100) [m(C„O)], 1569.7 (5), 1545.5 (5) [m(C@N) and
m(C@C)]; HRMS (ESI) calcd for C16H18NSO5W [M ꢀ H]ꢀ:
520.0410; found: 520.0429.
SEt
1
(OC)5W
2
H
3
4.12. (2s-cis,3Z,4s-cis,5E)-1,1,1,1,1-Pentacarbonyl-2-
ethylsulfanyl-6-phenyl-4-N-methylamino-1-tungsten-1,3,5-
hexatriene (18f), pentacarbonyl[(3-ethylsulfanyl-4-phenyl-
cyclopent-2-enylidene)-methyl- amine, N-W]tungsten(0)
[(1Z)-19f and (1E)-19f], pentacarbonyl[3-(methylamino)-
5-phenyl-penta-1,2,4-triene-1-ylidene]tungsten(0) (20f)
N
18d
4
5
6
7
4.11.1. Data for 18d
1H NMR (600 MHz, CDCl3, 233 K): d 10.00 (s, br,
3J(H,H) = 8.3 Hz, 1H; NH), 6.89 (dq, J(H,H) = 15.3 Hz,
3
(E)-N-Methyl-3-phenyl-acrylimidoyl chloride (5f), gener-
ated in situ from (2E)-N-methyl-3-phenyl acrylamide (4f,
332 mg, 2.0 mmol) and phosphorous oxychloride (306 mg,
2.0 mmol), was reacted with pentacarbonyl[1-(ethylsulfa-
nyl)eth-1-ylidene]tungsten(0) (1b, 412 mg, 1.0 mmol) as
described above at ꢀ78 ꢁC to give compound 18f (250 mg,
49%, Rf = 0.6 in 1:2 n-pentane/diethyl ether, red oil).
Compound 18f in CDCl3, 20 ꢁC was transformed into the
yellow compound (Z)-19f (195 mg, 35%, Rf = 0.6 in 10:1
n-pentane/diethyl ether, yellow oil) after short time. An equi-
librium between (Z)-19f and (E)-19f (Rf = 0.4 in 10:1 n-pen-
tane/diethyl ether) with a E/Z-ratio of 2:3 was established
after 14 d, 20 ꢁC. A more polar dark red to violet fraction
yielded compound 20f (109 mg, 22%, Rf = 0.6 in 1:1 dichlo-
romethane/diethyl ether, violet oil).
3J(H,H) = 6.9 Hz, 1H; 6-H), 6.72 (s, 1H; 3-H), 6.40 (dq,
3J(H,H) = 15.3 Hz, 4J(H,H) = 1.2 Hz, 1H; 5-H), 4.10
[d{sept}, 3J(H,H) = 8.3 Hz, 3J(H,H) = 6.9 Hz, 1H;
CH(CH3)2], 2.90 (q, 3J(H,H) = 7.5 Hz, 2H; SCH2CH3),
2.07 (dd, 3J(H,H) = 6.9 Hz, 4J(H,H) = 1.2 Hz, 3H; 7-
CH3), 1.47 [d, 3J(H,H) = 6.6 Hz, 6 H; CH(CH3)2], 1.32
(t, 3H; SCH2CH3); 13C NMR (150 MHz, CDCl3, 233 K):
d 224.2 (Cq; W@C), 202.9 and 198.7 [Cq, 1:4, trans- and
cis-CO; W(CO)5], 160.8 (Cq; C4), 143.7 (CH; C6), 124.0
(CH; C5), 115.1 (CH; C3), 47.3 (CH; NCH), 32.3
(SCH2CH3), 22.0 (CH3; NCH(CH3)2]), 19.9 (CH3; C7),
11.4 (SCH2CH3); IR (cyclohexane) [cmꢀ1 (%)]: m = 3201.1
(1) [m(N–H)], 2061.0 (30), 1935.1 (100), 1918.9 (70),
1906.8 (50) [m(C„O)], 1556.0 (5), 1508.4 (5); HRMS
~

2984
F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
[cmꢀ1 (%)]: m = 2066.4 (20), 1965.0 (5), 1925.3 (100),
~
SEt
2
1
1910.9 (50) [m(C„O)], 1606.1 (5), 1544.1 (5) [m(C@C) and
(OC)5W
m(C@N)]; IR (diffuse reflexion) [cmꢀ1 (%)]: m = 2065.6 (5),
~
3
H
N
1971.0 (3), 1897.1 (100), 1602.4 (4), 1541.7 (10); MS
(70 eV): m/z for 184W (%): 555 (30) [M]+, 471 (75) [M –
3CO]+, 442 (50) [M ꢀ 3CO ꢀ Et]+, 415 (40) [M – 5CO]+,
231 (100) [M ꢀ W(CO)5]+, 170 (70) [M ꢀ W(CO)5 ꢀ SEt]+;
HRMS (ESI) calcd for C19H17NSO5WNa [M + Na]+:
578.0253; found: 578.0237.
18f
4
6
Me
5
Ph
4.12.1. Data for 18f
1H NMR (600 MHz, CDCl3, 233 K): d 0.02 (q, br,
3J(H,H) = 5.6 Hz, 1H; NH), 7.65 (m, 2 H; o-CH Ph),
H
3
7.65 (d, J(H,H) = 16.1 Hz, 1H; CH-Ph), 7.51 (m, 3H; m/
N
CH3
p-CH Ph), 6.96 (d, 3J(H,H) = 16.1 Hz, 1H; CHCHPh),
6.86 (s, 1H; 3-H), 3.32 (d, 3J(H,H) = 5.6 Hz, 3 H;
NCH3), 2.95 (q, br, 2H; SCH2CH3), 1.34 (t, 3H;
SCH2CH3); 13C NMR (150 MHz, CDCl3, 233 K): d 225.4
(Cq; W@C), 202.9 and 198.5 [each Cq, 1:4, trans- and cis-
CO; W(CO)5], 163.3 (Cq; C4), 144.6 (CH; C6), 133.8 (Cq;
i-C Ph), 131.2 (CH; p-C Ph), 129.1 and 128.2 (CH; o-
and m-C Ph), 118.7 (CH; C5), 114.9 (CH; C3), 32.7
(SCH2CH3), 31.1 (CH2; NCH3), 11.4 (SCH2CH3); IR
•
•
(OC)5W
1
20f
2
3
4
5
6
Ph
4.12.3. Data for 20f
1H NMR (400 MHz, CDCl3, 300 K): d 10.36 (s, br, 1H;
NH), 7.98 (d, 3J(H,H) = 15.4 Hz, 1H; PhCH), 7.51 (m, 2H;
o-CH Ph), 7.28 (m, 3H; m- and p-CH Ph), 6.98 (d,
3J(H,H) = 15.4 Hz, 1H; PhCH@CH), 3.38 (s, 3H;
NCH3); 13C NMR (100 MHz, CDCl3, 300 K): d 203.3
and 197.4 [each Cq, 1:4, trans- and cis-CO; W(CO)5],
193.9 (Cq, dynamically broadened; W@C), 154.1 (Cq;
C4), 149.8 (CH; C6), 134.2 (Cq; i-C Ph), 131.2 (CH; p-
CH Ph), 129.0 and 128.6 (each CH; o- and m-CH Ph),
121.9 (CH; C5), 112.3 (Cq; C3), 34.1 (NCH3); IR (dichloro-
(cyclohexane) [cmꢀ1 (%)]: m = 2060.9 (40), 1936.3 (100),
~
1911.8 (60) [m(C„O)]; HRMS (ESI) calcd for
C19H17NSO5WNa [M + Na]+: 578.0229; found: 578.0231.
Ph
4
Ph
4
EtS
EtS
5
5
3
3
methane) [cmꢀ1 (%)]: m = 3386.7 (4) [m(N–H)], 2083.0 (1),
1
1
~
(Z
)-19f
(E)-19f
2
2
N
W(CO)5
1992.9 (35), 1929.8 (100) [m(C„O)], 1625.5 (7), 1565.3 (6),
1473.1 (10), 1451.4 (3); MS-ES (ESꢀ/NaBF4-addition):
m/z (%) = 580 (100) [M + BF4]ꢀ, 1073 (10) [2M + BF4]ꢀ.
N
CH3
H3C
(OC)5W
4.12.2. Data for (Z)-19f {(E)-19f} (obtained from a 10:6.5
Z/E mixture)
4.13. (E)-N-Propyl-3-phenyl-acrylimidoyl chloride (5g),
(2s-cis,3Z,4s-cis,5E)-1,1,1,1,1-Pentacarbonyl-2-
ethylsulfanyl-6-phenyl-4-N-propylamino-1-tungsten-1,3,5-
hexatriene (18g), pentacarbonyl[(3-ethylsulfanyl-4-phenyl-
cyclopent-2-enylidene)-propyl-amine, N-W]tungsten(0)
[(1Z)-19g and (1E)-19g], pentacarbonyl[3-
(propylamino)-5-phenyl-penta-1,2,4-triene-1-
ylidene]tungsten(0) (20g)
1H NMR (600 MHz, CDCl3, 298 K): d 7.36 {7.36} (m,
2H; m-CH Ph), 7.31 {7.31} (m, 1H; p-CH Ph), 7.15
{7.15} (m, 2H; o-CH Ph), 6.58 {6.26} (d, 4J(H,H) = 1.4 Hz
{1.4 Hz}, 1H; 2-H, NOE (+) with SCH2 {NOE (+) with
NCH3 and SCH2}), 4.12 {4.05} (m, 1H; 4-H), 3.54
{3.68} (s, 3H; NCH3, NOE (+) with 5-H2 {NOE (+) with
2-H}), 3.24 {3.40} (ddd,2J(H,H) = 18.0 Hz {18.0 Hz},
3J(H,H) = 7.6 Hz {7.6 Hz}, 5J(H,H) = 0.7 Hz {1.4 Hz},
1H; cis-5-H2, NOE (+) with 4-H, NCH3 and trans-5-H2
{NOE (+) with 4-H and trans-5-H2}), 2.95 {2.87} (q, 2H;
SCH2CH3), 2.64 {2.90} (ddd, 2J(H,H) = 18.0 Hz
{18.0 Hz}, 3J(H,H) = 2.6 Hz {2.6 Hz}, 5J(H,H) = 0.7 Hz
{1.4 Hz}, 1H; trans-5-H2), 1.38 {1.32} (t, 3H; SCH2CH3);
13C NMR (150 MHz, CDCl3, 298 K): d 202.5 and 199.0
{202.4 and 198.7} [each Cq, 1:4, trans- and cis-CO;
W(CO)5], 184.4 {184.0} (Cq; C@N), 173.1 {175.4} (Cq;
C3), 140.7 {140.5} (Cq; i-C Ph), 129.1 {129.0} (CH; m-C
Ph), 127.9 {127.8} (CH; p-C Ph), 127.2 {127.2} (CH; o-C
Ph), 126.2 {115.1} (CH; C2), 53.4 {53.9} (NCH3), 52.5
{51.3} (CH; C4), 40.8 {49.0} (CH2; C5), 27.2 {26.9}
(SCH2CH3), 13.2 {13.0} (SCH2CH3); IR (cyclohexane)
(E)-N-Propyl-3-phenyl-acrylimidoyl chloride (5g), gen-
erated in situ as described above from (2E)-N-propyl-
3-phenyl acrylamide (4g, 378 mg, 2.0 mmol) and phospho-
rous oxychloride (306 mg, 2.0 mmol) and pentacarbonyl-
[1-(ethylsulfanyl)eth-1-ylidene]tungsten(0) (1b, 412 mg,
1.0 mmol). Work-up gave red crystals of compound 18g
(328 mg, 56%, Rf = 0.3 in 7:3 n-pentane/diethyl ether). In
solution (CDCl3, 20 ꢁC) 18g was transformed into (Z)-
19g (Rf = 0.7 in 10:1 n-pentane/diethyl ether, yellow oil)
within 4 h. In CDCl3 (Z)-19g and (E)-19g (Rf = 0.5 in
10:1 n-pentane/diethyl ether, yellow oil) had an equilibrium
with a E/Z-ratio of 3:4 after 11 d at 20 ꢁC. A more polar
dark red to violet fraction yielded 20g (160 mg, 31%,
Rf = 0.7 in dichloromethane, violet oil).

F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
2985
(m, 2H; o-CH Ph), 6.60 {6.16} (d, 4J(H,H) = 1.4 Hz
{1.4 Hz}, 1H; 2-H), 4.10 {4.02} (m, 1H; 4-H), 3.61 {3.80}
(t {m}, 3J(H,H) = 8.4 Hz, 2H; NCH2), 3.25 {3.37} (dd,
N
5g
Ph
Cl
3
2J(H,H) = 17.9 Hz {17.9 Hz}, J(H,H) = 7.7 Hz {7.7 Hz},
3
1H; cis-5-H2), 2.93 {2.85} (q, J(H,H) = 7.4 Hz {7.4 Hz},
2H; SCH2CH3), 2.67 {2.87} (dd, 2J(H,H) = 17.9 Hz
{17.9 Hz}, 3J(H,H) = 2.6 Hz {2.6 Hz}, 1H; trans-5-H2),
1.68 {1.76} (m, 2H; NCH2CH2CH3), 1.36 {1.31} (t,
3J(H,H) = 7.4 Hz {7.4 Hz}, 3H; SCH2CH3), 0.94 {1.02} (t,
3J(H,H) = 7.4 Hz {7.4 Hz}, 3H; NCH2CH2CH3); 13C
NMR (100 MHz, CDCl3, 300 K): d 202.0 and 199.1 {202.0
and 198.8} [Cq, 1:4, trans- and cis-CO; W(CO)5], 183.7
{185.5} (Cq; C@N), 172.9 {174.8} (Cq; C3), 140.8 {140.6}
(Cq; i-C Ph), 129.1 {129.0} (CH; m-C Ph), 127.8 {127.7}
(CH; p-C Ph), 127.1 {127.1} (CH; o-C Ph), 126.8 {115.5}
(CH; C2), 67.4 {67.9} (CH2; NCH2), 52.5 {51.2} (CH; C4),
40.0 {49.5} (CH2; C5), 27.1 {26.8} (SCH2CH3), 22.8
{23.3} (NCH2CH2CH3), 13.2 {13.0} (SCH2CH3), 11.1
{11.1} (NCH2CH2CH3); IR (cyclohexane) [cmꢀ1 (%)]:
4.13.1. Data for 5g (obtained from a 1:1 mixture of the
amide and phosphorous oxychloride in CDCl3 after 48 h,
20 ꢁC; yield estimated according to NMR ca. 85%)
1H NMR (400 MHz, CDCl3, 300 K): d 8.02 (d, 3J(H,H) =
15.3 Hz, 1 H; PhCH), 7.82 (d, 3J(H,H) = 15.3 Hz, 1H;
PhCH@CH), 7.76 (m, 2H; o-CH Ph), 7.55 (m, 1H; p-CH
3
Ph), 7.46 (m, 2H; m-CH Ph), 3.87 (t, J(H,H) = 7.3 Hz; 2
3
H; NCH2), 1.95 (m, 2H; NCH2CH2), 1.08 (t, J(H,H) =
7.4 Hz, 3H; NCH2CH2CH3); 13C NMR (100 MHz, CDCl3,
300 K): d 167.8 (Cq; C@N), 154.5 (CH; PhCH), 133.3 (CH;
p-C Ph), 132.2 (Cq; i-C Ph), 130.0 (CH; o-C Ph), 129.1
(CH; m-C Ph), 117.1 (CH; CH@CH-Ph), 51.1 (CH2;
NCH2), 20.9 (NCH2CH2CH3), 10.9 (NCH2CH2CH3).
SEt
1
~
m = 2065.8 (20), 1963.5 (5), 1923.1 (100), 1909.3 (70)
2
(OC)5W
[m(C„O)], 1595.5 (5), 1545.2 (5) [m(C@C) and m(C@N)]; IR
(diffuse reflexion) [cmꢀ1 (%)]: m = 2064.8 (10), 1967.4 (3),
3
H
N
~
18g
1865.0 (100), 1591.3 (20), 1535.7 (30), 1493.5 (7), 1474.8
(5), 1453.9 (10), 1319.9 (8), 1073.3 (4); HRMS (ESI) calcd
for C21H21NSO5WNa [M + Na]+: 606.0543; found:
606.0534.
4
6
5
Ph
4.13.2. Data for 18g
H
N
1H NMR (400 MHz, CDCl3, 300 K): d 9.92 (s, br, 1H;
NH), 7.56 (m, 2H; o-CH Ph), 7.50 (d, br, 1H; CH-Ph),
7.45 (m, 3H; m/p-CH Ph), 6.94 (d, br, 1H; CHCHPh),
6.85 (s, 1H; 3-H), 3.52 (m, 2H; NCH2), 2.94 (q, 2 H;
SCH2CH3), 1.91 (m, 2H; NCH2CH2), 1.34 (t, 3H;
SCH2CH3), 1.08 (t, 3H; NCH2CH2CH3); 13C NMR
(100 MHz, CDCl3, 300 K): d 229.6 (Cq; W@C), 202.8 and
199.0 [each Cq, 1:4, trans- and cis-CO; W(CO)5], 162.5
(Cq; C4), 143.4 (CH; C6), 134.5 (Cq; i-C Ph), 130.9 (CH;
p-C Ph), 129.2 and 128.0 (CH; o- and m-C Ph), 120.2
(CH, br; C5), 115.6 (CH, br; C3), 47.0 (CH2; NCH2),
33.0 (SCH2CH3), 22.5 (NCH2CH2CH3), 11.8 (SCH2CH3),
11.4 (NCH2CH2CH3); IR (cyclohexane) [cmꢀ1 (%)]:
•
•
(OC)5W
1
20g
2
4
5
6
3
Ph
4.13.4. Data for 20g
1H NMR (500 MHz, CDCl3, 298 K): d 10.45 (s, br, 1H;
NH), 8.00 (d, 3J(H,H) = 15.4 Hz, 1H; PhCH), 7.52 (m, 2H;
o-CH Ph), 7.34 (m, 1H; p-CH Ph), 7.28 (m, 2H; m-CH Ph),
7.02 (m, 3J(H,H) = 15.4 Hz, 1H; PhCH@CH), 3.79 (m, 2H;
NCH2), 1.81 (m, 2H; NCH2CH2), 1.03 (t, 3H;
NCH2CH2CH3); 13C NMR (125 MHz, CDCl3, 298 K): d
203.3 and 197.4 [each Cq, 1:4, trans- and cis-CO;
W(CO)5], 190.8 (Cq, br; W@C); [compare: 191.0;
W(CO)6], 153.3 (Cq; C4), 149.9 (CH; C6), 134.2 (Cq; i-C
Ph), 131.1 (CH; p-CH Ph), 129.0 (CH; m-CH Ph), 128.7
(CH; o-CH Ph), 121.7 (CH; C5), 111.4 (Cq; C3), 49.5
(NCH2), 22.2 (NCH2CH2), 11.4 (NCH2CH2CH3); IR
(dichloromethane) [cmꢀ1 (%)]: ~m = 3377.3 (5) [m(N-H)],
2083.0 (2), 1993.2 (25), 1929.5 (100) [m(C„O)], 1625.6
(10), 1550.1 (10), 1470.4 (10), 1450.1 (10); IR (diffuse reflex-
~
m = 2060.7 (40), 1935.1 (100), 1917.7 (60) [m(C„O)];
HRMS (ESI) calcd for C21H20NSO5W [M ꢀ H]ꢀ:
582.0567; found: 582.0593.
Ph
4
Ph
4
EtS
EtS
5
5
3
3
1
1
(Z)-19g
(E )-19g
2
2
N
N
W(CO)5
(OC)5W
ion) [cmꢀ1 (%)]: m = 3358.1 (10) [m(N-H)], 2083.5 (1), 2002.5
~
4.13.3. Data for (Z)-19g {(E)-19g} (obtained from a 10:3
Z/E mixture)
1H NMR (400 MHz, CDCl3, 300 K): d 7.35 {7.35} (m,
2H; m-CH Ph), 7.29 {7.29} (m, 1H; p-CH Ph), 7.12 {7.12}
(40), 1968.8 (20), 1899.0 (100), 1870.7 (75), 1845.7 (40)
[m(C„O)], 1622.9 (10), 1555.3 (30); HRMS (ESI) calcd
for C19H15NO5WNa [M + Na]+: 544.0355; found:
544.0346.

2986
F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
4.14. Pentacarbonyl[allyl-(3-ethylsulfanyl-4-phenyl-
cyclopent-2-enylidene)- amine, N-W]tungsten(0) [(1Z)-
19h and (1E)-19h], pentacarbonyl[3-(allylamino)-5-
phenyl-penta-1,2,4-triene-1- ylidene]tungsten(0) (20h)
(SCH2CH3), 13.2 {12.9} (SCH2CH3); IR (cyclohexane)
[cmꢀ1 (%)]: m = 2066.4 (25), 1966.1 (5), 1925.1 (100),
~
1909.3 (50) [m(C„O)], 1594.7 (10), 1543.8 (10) [m(C@C)
and m(C@N)]; IR (diffuse reflexion) [cmꢀ1 (%)]: m = 2065.2
~
(10), 1968.4 (4), 1881.5 (100), 1591.5 (13), 1537.8 (15),
1493.9 (3), 1454.4 (4); HRMS (ESI) calcd for
C21H19NSO5WNa [M + Na]+: 604.0386; found: 604.0379.
(E)-N-Allyl-3-phenyl-acrylimidoyl chloride (5h), gener-
ated from (2E)-N-allyl-3-phenyl acrylamide (4h, 372 mg,
2.0 mmol) and phosphorous oxychloride (306 mg,
2.0 mmol) was reacted with pentacarbonyl[1-(ethylsulfa-
nyl)eth-1-ylidene]tungsten(0) (1b, 412 mg, 1.0 mmol). Reac-
tion with triethylamine (808 mg, 8.0 mmol) at ꢀ78 ꢁC and
work-up by flash chromatography at 20 ꢁC on silica gel
(40 · 1 cm, 1:1 n-pentane/diethyl ether) afforded a red com-
pound (Rf = 0.2 in 10:1 n-pentane/diethyl ether) which was
thermolabil and was transformed into compound (Z)-19h
(128 mg, 22%, Rf = 0.6 in 10:1 n-pentane/diethyl ether, yel-
low oil) within short time. Compounds (Z)-19h and (E)-19h
(Rf = 0.5 in 10:1 n-pentane/diethyl ether, yellow oil) were in
equilibrium in 7:10 E/Z-ratio after 14 d, 20 ꢁC in CDCl3. A
more polar dark red to violet fraction yielded compound
20h (55 mg, 11%, Rf = 0.5 in 1:1:1 n-pentane/diethyl
ether/dichloromethane, violet oil).
H
N
•
•
20h
(OC)5W
1
4
5
6
2
3
Ph
4.14.2. Data for 20h
1H NMR (400 MHz, CDCl3, 300 K): d 10.30 (s, br; 1H;
NH), 7.99 (d, 3J(H,H) = 15.4 Hz, 1H; PhCH), 7.53 (m, 2H;
o-CH Ph), 7.34 (m, 1H; p-CH Ph), 7.29 (m, 2H; m-CH Ph),
7.04 (m, 3J(H,H) = 15.4 Hz, 1H; PhCH@CH), 5.90 (m, 1H;
NCH2CH), 5.38 (d, br, 3J(H,H) = 15.4 Hz, 1H; trans-
3
NCH2CHCH2), 5.28 (d, br, J(H,H) = 10.2 Hz, 1H; cis-
NCH2CHCH2), 4.40 (m, 2H; NCH2).; 13C NMR
(100 MHz, CDCl3, 300 K): d 203.3 and 197.4 [each Cq,
1:4, trans- and cis-CO; W(CO)5], (Cq; W@C), [25] 152.8
(Cq; C4), 150.3 (CH; C6), 134.3 (Cq; i-C Ph), 131.2 (CH;
p-CH Ph), 130.7 (NCH2CH), 129.0 (CH; m-CH Ph),
128.7 (CH; o-CH Ph), 121.8 (CH; C5), 119.8
(NCH2CHCH2), (Cq; C3), [25] 50.0 (NCH2); IR (dichloro-
Ph
4
Ph
4
EtS
EtS
5
5
3
3
1
1
(Z )-19h
(E)-19h
W(CO)5
2
2
N
N
methane) [cmꢀ1 (%)]: m = 2083.0 (1), 1993.5 (30), 1929.0
(OC)5W
~
(100) [m(C„O)]; HRMS (ESI) calcd for C19H13NO5WNa
4.14.1. Data for(Z)-19h{(E)-19h} (obtained from a 10:4
mixture)
[M + Na]+: 542.0198; found: 542.0181.
1H NMR (500 MHz, CDCl3, 298 K) d 7.35 {7.35} (m,
2H; m-CH Ph), 7.30 {7.30} (m, 1H; p-CH Ph), 7.11 {7.13}
(m, 2H; o-CH Ph), 6.66 {6.11} (d, 4J(H,H) = 1.4 Hz
4.15. Pentacarbonyl[(3-ethylsulfanyl-4-phenyl-cyclopent-2-
enylidene)-phenyl-amine, N-W]tungsten(0) [(1 Z)-19i and
(1E)-19i], pentacarbonyl[3-(phenylamino)-5-phenyl-penta-
1,2,4-triene-1-ylidene]tungsten(0) (20i), (E)-3,N-diphenyl-
thioacrylimidic acid ethyl ester (21i)
3
{1.4 Hz}, 1H; 2-H), 5.83 {5.89} (ddt, J(H,H) = 17.3 Hz
{17.3 Hz}, 3J(H,H) = 10.5 Hz {10.5 Hz}, 3J(H,H) = 4.7 Hz
{4.7 Hz}, 1H; CH2CH=CH2), 5.28 {5.34} (ddt,2J(H,H) =
3
4
1.1 Hz {1.1 Hz}, J(H,H) = 10.5 Hz {10.5 Hz}, J(H,H) =
1.9 Hz {1.9 Hz}, 1H; cis-CH2CH@CH2), 5.11 {5.14} (ddt,
(E)-N-Phenyl-3-phenyl-acrylimidoyl chloride (5i), gener-
ated in situ from (2E)-N-phenyl-3-phenyl acrylamide (4i,
446 mg, 2.0 mmol) and phosphorous oxychloride (306 mg,
2.0 mmol) at 20 ꢁC, 5 d, was reacted with pentacarbonyl[1-
(ethylsulfanyl)eth-1-ylidene]tungsten(0) (1b, 412 mg, 1.0
mmol) and triethylamine (808 mg, 8.0 mmol) at ꢀ78 ꢁC.
Work-up at 20 ꢁC with silica gel (40 · 1 cm, 1:1 n-pentane/
diethyl ether) gave colorless compound 21i (82 mg, 37%,
Rf = 0.8 in 10:1 n-pentane/diethyl ether) and a yellow com-
pound (Z)-19i (13 mg, 2%, Rf = 0.5 in 10:1 n-pentane/
diethyl ether, yellow oil). Equilibration of (Z)-19i and (E)-
19i (Rf = 0.4 in 10:1 n-pentane/diethyl ether) is accompanied
2J(H,H) = 1.1 Hz {1.1 Hz}, J(H,H) = 17.3 Hz {17.3 Hz},
3
4J(H,H) = 1.9 Hz {1.9 Hz}, 1H; trans- CH2CH@CH2),
4.38 {4.55} (m, 2H; NCH2), 4.10 {4.06} (m, 1H; 4-H),
2
3
3.25 {3.46} (dd, J(H,H) = 18.2 Hz {18.2 Hz}, J(H,H) =
7.6 Hz {7.6 Hz}, 1H; cis-5-H2), 2.96 {2.82} (q, 2H;
SCH2CH3), 2.67 {2.96} (dd, 2J(H,H) = 18.2 Hz {18.2 Hz},
3J(H,H) = 2.6 Hz {2.6 Hz}, 1H; trans-5-H2), 1.38 {1.30}
3
(t, J(H,H) = 7.4 Hz {7.4 Hz}, 3H; SCH2CH3); 13C NMR
(100 MHz, CDCl3, 300 K): d 202.2 and 199.0 {202.1 and
198.7} [each Cq, 1:4, trans- and cis-CO; W(CO)5], 185.6
{185.2} (Cq; C@N), 174.2 {175.7} (Cq; C3), 140.5 {140.4}
(Cq; i-C Ph), 132.3 {133.0} (CH; CH2CH@CH2), 129.1
{129.1} (CH; m-C Ph), 127.8 {127.8} (CH; p-C Ph), 127.2
{127.2} (CH; o-C Ph), 126.3 {116.2} (CH; C2), 116.6
{116.9} (CH2; CH2CH=CH2), 67.3 {67.8} (CH2; NCH2),
52.6 {51.3} (CH; C4), 40.2 {49.2} (CH2; C5), 27.3 {26.9}
1
by strong decomposition. H NMR data of (E)-19i were
obtained from a sample freshly collected by chromatogra-
phy. A polar deep blue fraction (30 mg, Rf = 0.3 in 1:1:1
n-pentane/diethyl ether/dichloromethane) was not charac-
terized completely. A structure 20i is proposed on the basis
of an exact mass determination.

F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
2987
CDCl3, 300 K): d 163.4 (Cq; C@N), 150.5 (Cq; i-C N-Ph),
137.8 (CH; Ph-CH), 135.4 (Cq; i-C Ph), 129.3, 128.8,
128.7, 127.5 (each CH, 1:2:2:2; m-C N-Ph and o-, m-, p-C
Ph), 123.5 (CH; p-C N-Ph), 121.4 (CH; PhCHCH), 120.9
(CH; o-C N-Ph), 24.1 (SCH2), 14.2 (SCH2CH3); IR (cyclo-
Ph
4
Ph
4
EtS
EtS
5
5
3
3
1
1
(E )-19i
(Z )-19i
2
2
Ph
N
W(CO)5
N
hexane) [cmꢀ1 (%)]: m = 1627.3 (30), 1580.5 (100) [m(C@N)];
~
Ph
HRMS (ESI) calcd for C17H18NS [M + H]+: 268.1154;
(OC)5W
found: 268.1144.
4.15.1. Data for (Z)-19i{(E)-19i} (1H NMR data could be
collected only partially from a 20:1 mixture due to facile
decomposition)
4.16. Pentacarbonyl[(3-ethylsulfanyl-4-methyl-cyclopent-2-
enylidene)-methyl- amine, N-W]tungsten(0) [(1Z)-19j and
(1E)-19j]
1H NMR (500 MHz, CDCl3, 298 K): d 7.36 (m, 2H; m-
CH N-Ph), 7.33 (m, 2H; m-CH Ph), 7.27 (m, 1H; p-CH Ph),
7.13 (m, 1H; p-CH N-Ph), 7.08 (m, 2H; o-CH Ph), 6.88 (m,
(E)-N-Methyl-but-2-ene-1-carboximidoyl chloride (5j),
generated in situ from (E)-but-2-enonic acid methylamide
(4j, 198 mg, 2.0 mmol) and phosphorous oxychloride
(306 mg, 2.0 mmol), was reacted with pentacarbonyl[1-(eth-
ylsulfanyl)eth-1-ylidene]tungsten(0) (1b, 412 mg, 1.0 mmol)
and triethylamine (808 mg, 8.0 mmol) at ꢀ78 ꢁC. Work-up
at 20 ꢁC on silica gel (40 · 1 cm, 1:1 n-pentane/diethyl ether)
afforded a red thermolabile compound (Rf = 0.3 in 1:1 n-
pentane/diethyl ether) which was transformed into yellow
compound (Z)-19j (130 mg, 26%, Rf = 0.7 in 10:1 n-pen-
tane/diethyl ether, yellow oil) after a short time. A 2:3 equi-
librium (Z)-19j and (E)-19j was achieved at 20 ꢁC, 14 d in
CDCl3 (Rf = 0.6 in 10:1 n-pentane/diethyl ether).
4
2H; o-CH Ph), 6.77 {5.47} (d, J(H,H) = 1.4 Hz {1.4 Hz},
1H; 2-H), 4.03 {4.16} (m, 1H; 4-H), 2.84 {3.59} (dd,
3
2J(H,H) = 18.9 Hz {18.3 Hz}, J(H,H) = 7.4 Hz {7.5 Hz},
3
1H; cis-5-H2), 3.02 {2.58} (q, J(H,H) = 7.4 Hz {7.6 Hz},
2H; SCH2CH3), 2.28 {3.06} (dd,2J(H,H) = 18.9 Hz
{18.3 Hz}, 3J(H,H) = 2.8 Hz {2.6 Hz}, 1H; trans-5-H2),
1.42 {1.13} (t, 3J(H,H) = 7.4 Hz {7.6 Hz}, 3H; SCH2CH3);
13C NMR (125 MHz, CDCl3, 298 K): d 203.2 and 198.9
[Cq, 1:4, trans- and cis-CO; W(CO)5], 185.5 (Cq; C@N),
177.0 (Cq; C3), 155.7 (Cq; i-C N-Ph), 140.3 (Cq; i-C CH-
Ph), 129.5 and 129.4 (CH; m-C N-Ph), 129.1 (CH; m-C
CH-Ph), 127.8 (CH; p-C CH-Ph), 127.1 (CH; o-C CH-
Ph), 125.9 (CH; p-C N-Ph), 125.0 (CH; C2), 120.6 and
120.5 (each CH; o-C N-Ph), 52.7 (CH; C4), 42.1 (CH2;
C5), 27.4 (SCH2CH3), 13;2 (SCH2CH3); IR (cyclohexane)
CH3
4
CH3
4
EtS
EtS
5
5
3
3
[cmꢀ1 (%)]: m = 2067.0 (25), 1970.6 (10), 1941.1 (50),
1
1
~
(Z )-19j
(E)-19j
2
2
1929.1 (100), 1923.4 (80), 1907.7 (50) [m(C„O)], 1585.5
(10), 1538.7 (10) [m(C@C) and m(C@N)]; HRMS (ESI) calcd
for C24H19NSO5WNa [M + Na]+: 640.0378; found:
640.0378.
N
W(CO)5
N
CH3
H3C
(OC)5W
4.16.1. Data for (Z)-19j{(E)-19j} (obtained from a 10:4
mixture)
H
1H NMR (500 MHz, CDCl3, 298 K) d 6.35 {6.07} (d,
4J(H,H) = 1.3 Hz {1.3 Hz}, 1H; 2-H, NOE (+) with SCH2
{NOE (+) with NCH3 and SCH2}), 3.52 {3.58} (s, 3H;
NCH3, NOE (+) with 5-H2 {NOE (+) with 2-H}), 3.06
N
Ph
6
•
•
(OC)5W
1
20i
2
3
4
5
Ph
3
{3.04} (‘‘t’’, J(H,H) = 7.1 Hz, 1H; cis-5-H2), 2.95 {3.11}
(m, 1H; CHCH3), 2.97 {2.92} (q, 2H; SCH2CH3), 2.25
{2.45} (‘‘d’’, 2J(H,H) = 17.7 Hz {17.7 Hz}, 1H; trans-5-
H2, NOE (+) with NCH3, cis-5-H2 and 4-H NOE (+) with
4.15.2. Data for 20i
HRMS (ESI) calcd for C22H12NO5W [M ꢀ H]ꢀ:
554.0223; found: 554.0242.
3
4-H and cis-5-H2), 1.43 {1.40} (t, J(H,H) = 7.4 Hz, 3H;
SCH2CH3), 1.24 {1.26} (d, 3J(H,H) = 7.1 Hz, 3 H;
CHCH3); 13C NMR (125 MHz, CDCl3, 298 K): d 202.6
and 199.0 {202.5 and 198.9} [each Cq, 1:4, trans- and cis-
CO; W(CO)5], 184.5 {184.0} (Cq; C@N), 175.2 {177.3}
(Cq; C3), 124.7 {114.0} (CH; C2), 53.2 {53.5} (NCH3),
41.4 {40.2} (CH; C4), 39.1 {47.8} (CH2; C5), 26.9 {26.7}
(SCH2CH3), 20.6 {20.5} (CHCH3), 13.3 {13.1} (SCH2CH3);
IR (cyclohexane) [cmꢀ1 (%)]: ~m = 2066.3 (15), 1964.6 (5),
1924.7 (100), 1909.7 (40) [m(C„O)], 1606.7 (5), 1545.5 (5)
[m(C@C) and m(C@N)]; HRMS (ESI) calcd for
C14H15NSO5WNa [M + Na]+: 516.0072; found: 516.0057.
NPh
21i
Ph
SEt
4.15.3. Data for 21i
1H NMR (400 MHz, CDCl3, 300 K): d 7.43 (d,
3J(H,H) = 16.3 Hz, 1H; PhCH), 7.30 (m, 7 H; m-CH N-
Ph and o-, m-, p-CH Ph), 7.08 (m, 1H; p-CH N-Ph), 6.83
(m, 2H; o-CH N-Ph), 6.69 (d, 3J(H,H) = 16.3 Hz, 1H;
PhCHCH), 3.12 (q, 3J(H,H) = 7.4 Hz, 2H; SCH2), 1.38
(t, 3J(H,H) = 7.4 Hz; SCH2CH3); 13C NMR (100 MHz,

2988
F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
4.17. Pentacarbonyl[(3-ethylsulfanyl-4-methyl-cyclopent-2-
enylidene)-propyl-amine, N-W]tungsten(0) [(1Z)-19k and
(1E)-19k]
References
[1] E.O. Fischer, A. Maasbo¨l, Angew. Chem. 76 (1964) 645;
Angew. Chem., Int. Ed. Engl. 3 (1964) 580.
[2] (a) E.O. Fischer, U. Klabunde, J. Am. Chem. Soc. 89 (1967) 7141–
7142;
(E)-N-Propyl-but-2-ene-1-carboximidoyl chloride (5k),
generated in situ from (E)-but-2-enonic acid propylamide
(4k, 254 mg, 2.0 mmol) and phosphorous oxychloride
(306 mg, 2.0 mmol) was reacted with pentacarbonyl[1-(eth-
ylsulfanyl)eth-1-ylidene]tungsten(0) (1b, 412 mg, 1.0 mmol)
and triethylamine (808 mg, 8.0 mmol) at ꢀ78 ꢁC. Work-up
at 20 ꢁC on silica gel (40 · 1 cm, 1:1 n-pentane/diethyl ether)
afforded yellow compound (Z)-19k (55 mg, 11%, Rf = 0.6 in
10:1 n-pentane/diethyl ether, yellow oil), which in CDCl3
achieved a 9:10 equilibrium of (Z)-19k and (E)-19k (Rf =
0.5 in 10:1 n-pentane/diethyl ether) after 14 d, 20 ꢁC.
(b) E.O. Fischer, V. Kiener, Angew. Chem. 79 (1967) 982;
(c) E.O. Fischer, M. Leupold, C.G. Kreiter, J. Muller, Chem. Ber.
105 (1972) 150–161;
¨
(d) E.O. Fischer, Pure Appl. Chem. 30 (1972) 353–372.
[3] (a) K.H. Do¨tz, Angew. Chem. 96 (1984) 573–594;
Angew. Chem., Int. Ed. Engl. 23 (1984) 587–608;
(b) W.D. Wulff, in: B.M. Trost, I. Fleming (Eds.), Comprehensive
Organic Synthesis, vol. 5, Pergamon, New York, 1991, pp. 1065–
1113;
(c) W.D. Wulff, in: E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry II, vol. 12, Pergamon,
New York, 1995, pp. 469–547;
(d) M.D. Doyle, in: E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry II, vol. 12, Pergamon,
New York, 1995, pp. 387–420;
(e) W.D. Wulff, in: L.S. Liebeskind (Ed.), Advances in Metal–
Organic Chemistry, vol. 1, JAI Press, Greenwich, CT, 1989;
(f) D.F. Harvey, D.M. Sigano, Chem. Rev. 96 (1996) 271–288;
Me
4
Me
4
EtS
EtS
5
5
3
3
1
1
(E )-19k
)-19k
(Z
2
2
N
W(CO)5
N
(g) H.-W. Fruhauf, Chem. Rev. 97 (1997) 523–596;
¨
(h) A. De Meijere, H. Schirmer, M. Duetsch, Angew. Chem. 112
(2000) 4124–4162;
(OC)5W
Angew. Chem., Int. Ed. 39 (2000) 3964–4002;
(i) K.H. Do¨tz, Pure Appl. Chem. 55 (1983) 1689–1706;
(j) Y.-T. Wu, T. Kurahashi, A. De Meijere, J. Organomet. Chem. 690
(2005) 5900–5911;
4.17.1. Data for (Z)-19k{(E)-19k}
1H NMR (400 MHz, CDCl3, 300 K): d 6.37 {5.96} (d,
3J(H,H) = 1.2 Hz {1.2 Hz}, 1H; 2-H), 3.60 {3.71} (m, 1H;
NCH2), 3.03 {3.14} (m, 1H; CHCH3), 2.98 {3.09} (dd,
´
´
´
(k) J. Barluenga, F. Rodrıguez, J.F. Fananas, J. Florez, Topics
˜
Organomet. Chem. 13 (2004) 59–121;
(l) G.-G. Mar, M.J. Mancheno, M.A. Sierra, Acc. Chem. Res. 38
˜
(2005) 44–53;
3
2J(H,H) = 17.2 Hz {17.6 Hz}, J(H,H) = 7.0 Hz {7.1 Hz},
3
1H; cis-5-H2), 2.96 {2.91} (q, J(H,H) = 7.3 Hz {7.4 Hz},
2H; SCH2CH3), 2.28 {2.43} (dd, 2J(H,H) = 17.2 Hz
{17.6 Hz}, 3J(H,H) = 2.0 Hz {2.4 Hz}, 1H; trans-5-H2),
1.66 {1.66} (m, 2H; NCH2CH2CH3); 1.42 {1.40} (t,
3J(H,H) = 7.3 Hz {7.4 Hz}, 3H; SCH2CH3), 1.24 {1.26}
(d, 3J(H,H) = 7.0 Hz, 3H; CHCH3); 0.97 {0.97} (t, 3H;
NCH2CH2CH3); 13C NMR (150 MHz, CDCl3, 300 K): d
202.2 and 199.1 {202.3 and 198.9} [each Cq, 1:4, trans-
and cis-CO; W(CO)5], 183.7 {183.4} (Cq; C@N), 174.9
{176.7} (Cq; C3), 125.4 {114.2} (CH; C2), 67.3 {67.6}
(CH; NCH2), 41.4 {40.0} (CH; C4), 38.2 {48.3} (CH2;
C5), 26.9 {26.6} (SCH2CH3), 22.8 {23.2} (CH2;
NCH2CH2CH3]), 20.6 {20.5} (CH3; CHCH3), 13.3 {13.1}
(SCH2CH3), 11.3 {11.2} (CH3; NCH2CH2CH3); IR (cyclo-
(m) J. Barluenga, Pure Appl. Chem. 74 (2002) 1317–1325;
(n) H. Rudler, A. Parlier, Trends Organomet. Chem. 3 (1999) 113–
164;
(o) M.A. Schwindt, J.R. Miller, L.S. Hegedus, J. Organomet. Chem.
413 (1991) 143–153;
(p) D.B. Grotjahn, K.H. Do¨tz, Synlett 6 (1991) 381–390;
(q) L.S. Hegedus, Pure Appl. Chem. 62 (1990) 691–698.
[4] (a) C.T. Lam, C.V. Senoff, J. Organomet. Chem. 70 (1974) 273–
281;
(b) R. Aumann, J. Schro¨der, Chem. Ber. 123 (1990) 2053–2058;
(c) R. Aumann, J. Schro¨der, J. Organomet. Chem. 378 (1989) 57–65;
(d) K.H. Do¨tz, V. Leue, J. Organomet. Chem. 407 (1991) 337–351.
[5] H.G. Raubenheimer, G.J. Kruger, A. Lombard, J. Organomet.
Chem. 240 (1982) C11–C14.
[6] (a) H.G. Raubenheimer, G.J. Kruger, Ch.F. Marais, R. Otte, J.T.Z.
Hattingh, Organometallics 7 (1988) 1853–1858;
(b) H.G. Raubenheimer, G.J. Kruger, L. Linford, Ch.F. Marais, R.
Otte, J.T.Z. Hattingh, A. Lombard, J. Chem. Soc. Dalton Trans.
(1989) 1565–1577.
hexane) [cmꢀ1 (%)]: m = 2065.6 (25), 1963.2 (5),1924.2 (100),
~
1909.3 (70) [m(C„O)], 1597.4 (5), 1547.1 (5) [m(C@N) and
m(C@C)]; HRMS (ESI) calcd for C16H19NSO5WNa
[M + Na]+: 544.0386; found: 544.3384.
[7] (a) H.G. Raubenheimer, E.O. Fischer, U. Schubert, C. Kruger, Yi-
¨
H. Tsay, Angew. Chem. 93 (1981) 1103–1105;
Angew. Chem., Int. Ed. Engl. 20 (1981) 1055;
(b) H.G. Raubenheimer, G.J. Kruger, A. Lombard, L. Linford, J.C.
Viljoen, Organometallics 4 (1985) 275–284.
5. Supplementary material
[8] (a) R. Aumann, J. Schro¨der, J. Organomet. Chem. 378 (1989) 185–
197;
(b) F.R. Kreißl, E.O. Fischer, C.G. Kreiter, H. Fischer, Chem. Ber.
106 (1973) 1262–1276.
[9] R. Aumann, J. Schro¨der, H. Heinen, Chem. Ber. 123 (1990) 1369–
1374.
CCDC 622534 and 622535 contain the supplementary
crystallographic data for 13a and 18b. These data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/
conts/retrieving.html, or from the Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@
ccdc.cam.ac.uk.
[10] R. Aumann, J. Schro¨der, F. Nitsche, Unpublished results.
[11] B. Karatas, H. Kryspin, R. Aumann, In preparation.

F. Nitsche et al. / Journal of Organometallic Chemistry 692 (2007) 2971–2989
2989
¨
[12] (a) C.P. Casey, R.A. Boggs, R.L. Anderson, J. Am. Chem. Soc. 94
(4) (1972) 8947–8949;
[19] S. Unaldi, R. Aumann, R. Fro¨hlich, Chem. Eur. J. 9 (2003) 3300–
3309.
(b) R. Aumann, H. Heinen, Chem. Ber. 120 (1987) 537–540.
[13] W.D. Wulff, S.R. Gilbertson, J. Am. Chem. Soc. 107 (1985) 503–505.
[14] (a) R. Aumann, B. Jasper, M. La¨ge, B. Krebs, Organometallics 13
(1994) 3510–3516;
[20] Many thanks to Timo Wattjes for his support in the preparation of
the cyclopentenimines.
[21] For characteristic IR signals of the W(CO)5 coordinated to the
nitrogen atom of an imine see: He-P. Wu, R. Aumann, R. Fro¨hlich,
E. Wegelius, P. Saarenketo, Organometallics 19 (2000) 2373–2381.
[22] (a) E.O. Fischer, H.J. Kalder, A. Frank, F.H. Ko¨hler, G. Huttner,
Angew. Chem. 88 (1976) 683–684;
(b) C.P. Casey, R.A. Boggs, D.F. Marten, J.C. Calabrese, J. Chem.
Soc., Chem. Comm. (1973) 243–244;
(c) C.P. Casey, W.R. Brunsvold, D.M. Scheck, Inorg. Chem. 16
(1977) 3059–3063.
(b) R. Aumann, Chem. Ber. 127 (1994) 725–729;
[15] L.S. Hegedus, Pure Appl. Chem. 55 (1983) 1745–1748.
[16] L. Lattuada, E. Licandro, A. Papagni, St. Maiorana, A.Ch. Villa, C.
Guastini, J. Chem. Soc., Chem. Commun. (1988) 1092–1093.
[17] (a) R. Aumann, P. Hinterding, Chem. Ber. 123 (1990) 611–620;
(b) R. Aumann, P. Hinterding, Chem. Ber. 123 (1990) 2047–2051;
(c) R. Aumann, D. Vogt, X. Fu, R. Fro¨hlich, P. Schwab, Organo-
metallics 21 (2002) 1637–1645;
(c) H. Fischer, D. Reindl, G. Roth, Z. Naturforsch. 49b (1994) 1207–
1214.
[23] Not observed or equal to the signal of the major isomer.
[24] Data sets were collected with a Nonius KappaCCD diffractometer,
equipped with a Nonius FR591 rotating-anode generator. Programs
used: data collection: COLLECT (Nonius B.V., 1998); data reduc-
tion: Denzo-SMN (Z. Otwinowski, W. Minor, Methods Enzymol.
276 (1997) 307–326); absorption correction: SORTAV (R.H. Blessing,
Acta Crystallogr. Sect. A 51 (1995) 33–37; R.H. Blessing, J. Appl.
Cryst. 30 (1997) 421–426); structure solution: SHELXS-97 (G.M.
Sheldrick, Acta Crystallogr. Sect. A 46 (1990) 467–473); structure
refinement: (SHELXL-97, G.M. Sheldrick, Universita¨t Go¨ttingen,
1997); graphics: SCHAKAL (E. Keller, Universita¨t Freiburg, 1997).
[25] Not detected at ambient temperature due to dynamic line
broadening.
(d) R. Aumann, X. Fu, D. Vogt, R. Fro¨hlich, O. Kataeva,
Organometallics 21 (2002) 2736–2742, and references therein;
(e) R. Aumann, X. Fu, Chr. Holst, R. Fro¨hlich, Organometallics 21
(2002) 4356–4368.
[18] It should be noted that 1,4-adducts were not obtained with imidoyl
chlorides 5 derived from a,b-unsaturated secondary amides, even
though 1,4-adducts were generated from a,b-unsaturated tertiary
amides: F. Nitsche, R. Aumann, R. Fro¨hlich, in preparation.