Organic syntheses via transition metal complexes. 104. Cyclopentadienyl thiolacylates from (1-alkynyl)carbene complexes (M = Cr, W): sulfur-centered fragmentation of ligand side chains

Article abstract of DOI:10.1021/om000107v

Cyclopentadienes containing sulfur substituents were generated by addition of sulfur nucleophiles to [1-alkynyl-2-(cycloalk-1-enyl)]carbene complexes 1a-f (M = W, Cr). Cyclopentadienyl thiol(NH-imino)acylate-N complexes 12b-d,f,g were obtained in 82-95% yields by addition of thioamides RC(=S)NH₂ (10; R = Ph, Me) to (1-alkynyl)carbene complexes 1 at 20°C (20 min). Compounds 12 on thermolysis at 50°C gave cyclopentee-1-thione complexes 9 and nitriles 13 by a sulfur-centered fragmentation of the ligand side chain. Addition of thioamide MeC(=S)NHPh (16) to (1-alkynyl)carbene complexes 1 afforded thermally stable cyclopentadienyl thiol(NPh-imino)acylate-N complexes 17b,c in 94-96% yield. Valence isomers 18a-c of the latter compounds were generated in 83-89% yields, if the reaction was performed in the presence of a base, e.g. triethylamine. Addition of thiocarboxylic acids 6a,b to tungsten (1-alkynyl)carbene complexes 1a,b at 20°C produced cyclopentene-1-thione complexes 9a,b. Addition of thiocarboxylic acids 6a,b to the tungsten (1-alkynyl)carbene complex 19 at 20°C afforded 4-(S-thioacyl)-1-tungsta-1,3-butadienes 20.

Full text of DOI:10.1021/om000107v

Organometallics 2000, 19, 2373-2381
2373
Or ga n ic Syn th eses via Tr a n sition Meta l Com p lexes. 104.1
Cyclop en ta d ien yl Th iola cyla tes fr om (1-Alk yn yl)ca r ben e
Com p lexes (M ) Cr , W): Su lfu r -Cen ter ed F r a gm en ta tion
of Liga n d Sid e Ch a in s
He-Ping Wu, Rudolf Aumann,* Roland Fro¨hlich,† Elina Wegelius,† and
Pauli Saavenketo†
Organisch-Chemisches Institut der Universita¨t Mu¨nster, Corrensstrasse 40,
D-48149 Mu¨nster, Germany
Received February 7, 2000
Cyclopentadienes containing sulfur substituents were generated by addition of sulfur
nucleophiles to [1-alkynyl-2-(cycloalk-1-enyl)]carbene complexes 1a -f (M ) W, Cr). Cyclo-
pentadienyl thiol(NH-imino)acylate-N complexes 12b-d ,f,g were obtained in 82-95% yields
by addition of thioamides RC(dS)NH2 (10; R ) Ph, Me) to (1-alkynyl)carbene complexes 1
at 20 °C (20 min). Compounds 12 on thermolysis at 50 °C gave cyclopentene-1-thione
complexes 9 and nitriles 13 by a sulfur-centered fragmentation of the ligand side chain.
Addition of thioamide MeC(dS)NHPh (16) to (1-alkynyl)carbene complexes 1 afforded
thermally stable cyclopentadienyl thiol(NPh-imino)acylate-N complexes 17b,c in 94-96%
yield. Valence isomers 18a -c of the latter compounds were generated in 83-89% yields, if
the reaction was performed in the presence of a base, e.g. triethylamine. Addition of
thiocarboxylic acids 6a ,b to tungsten (1-alkynyl)carbene complexes 1a ,b at 20 °C produced
cyclopentene-1-thione complexes 9a ,b. Addition of thiocarboxylic acids 6a ,b to the tungsten
(1-alkynyl)carbene complex 19 at 20 °C afforded 4-(S-thioacyl)-1-tungsta-1,3-butadienes 20.
Sch em e 1. Cyclop en ta d ien e Rin gs by Ad d ition of
Oxygen Nu cleop h iles to (1-Alk yn yl)ca r ben e
Com p lex 1a
In tr od u ction
(1-Alkynyl)carbene complexes (CO)5MdC(OEt)CtCR
(M ) Cr, W) have been applied as stoichiometric
reagents in a number of high-yield transformations,
which could be potentially useful to organic synthesis.2
We recently reported on the formation of cyclopentadi-
ene rings by π-cyclization of 1-metalla-1,3,5-hexatrienes,3
which were readily derived from (1-alkynyl)carbene
complexes 1 by addition of protic nucleophiles NuH.4,5
To date, formation of cyclopentadienes has been found
to be triggered by addition of secondary amines R2NH,
secondary phosphines R2PH (R ) t-Bu, c-C6H11),6 and
oxygen nucleophiles7 ROH (R ) Ph, 1-Napht, MeCO,
PhCH2CO, PhCO, 4-t-BuC6H4CO), respectively, to (1-
alkynyl)carbene complexes 1. While nitrogen or phos-
* To whom correspondence should be addressed. Fax: ++49 251
833 6502. E-mail: aumannr@uni-muenster.de.
† Crystal structure analyses.
(1) Part 103: Aumann, R.; Ko¨ssmeier, M.; Roths, K.; Fro¨hlich, R.
Tetrahedron, in press.
(2) For a recent review on (1-alkynyl)carbene complexes see: Au-
mann, R.; Nienaber, H. Adv. Organomet. Chem. 1997, 41, 163-242.
(3) For a recent review on 1-metalla-1,3,5-hexatrienes and related
compounds see: Aumann, R. Eur. J . Org. Chem. 2000, 17-31.
(4) For a recent review on the preparation of five-membered car-
bocyclic rings from Fischer carbene complexes see: Herndon, J . W.
Tetrahedron 2000, 56, 1257-1280.
(5) For related studies, in which 1-metalla-1,3,5-trienes were gener-
ated by addition of dienes to (1-alkynyl)carbene complexes, see:
Barluenga, J .; Aznar, F.; Barluenga, S.; Ferna´ndez, M.; Mart´ın, A.;
Garc´ıa-Granda, S.; Pinera-Nicola´s A. Chem. Eur. J . 1998, 4, 2280-
2298.
phorus nucleophiles led to production of cyclopentadiene
complexes, oxygen nucleophiles gave highly reactive
metal-free cyclopentadienes, e.g. 1-acyl-3-alkoxy cyclo-
pentadienes 3. The latter compounds underwent a
cascade of reactions initiated by spontaneous formation
of tricyclic [2 + 2] cycloadducts 4 with (1-alkynyl)-
carbene complex 1a , which could be subsequently
transformed into pentacyclic compounds 5 by thermally
induced fragmentation (Scheme 1).7
(6) Aumann, R.; Fro¨hlich, R. Organometallics 1999, 18, 1369-1380.
(7) Wu, H.; Aumann, R.; Fro¨hlich, R. Eur. J . Org. Chem. 2000,
1183-1192.
We now wish to report on the generation of cyclopen-
tadienes containing sulfur substituents, such as thiol-
10.1021/om000107v CCC: $19.00 © 2000 American Chemical Society
Publication on Web 05/17/2000

2374 Organometallics, Vol. 19, No. 12, 2000
Wu et al.
Sch em e 2. (Cyclop en ten e-1-th ion e) Com p lexes by
F r a gm en ta tion of Cyclop en ta d ien e Th iola cyla te
Com p lexes
F igu r e 1. Molecular structure of hexahydropentalene-1-
thione complex 9a . Selected bond lengths (Å) and angles
(deg): W-S1 ) 2.543(2), S1-C2 ) 1.669 (4), C2-C3 )
1.397 (5), C2-C9 ) 1.513 (5), C3-C4 ) 1.360(5), C4-O10
) 1.318(4), C4-C5 ) 1.494(5), C5-C6 ) 1.539(6), C5-C9
) 1.547(5), C6-C7 ) 1.50(6), C7-C8 ) 1.511(7), C8-C9
) 1.542(6); C2-S1-W ) 115.7(1); C3-C2-C9 ) 110.4(3),
C3-C2-S1 ) 128.9(3), C9-C2-S1 ) 120.6(3), C4-C3-
C2 ) 108.9(3), O10-C4-C3 ) 130.0(4), O10-C4-C5 )
116.1(3), C3-C4-C5 ) 113.8(3), C4-C5-C6 ) 112.0(4),
C4-C5-C9 ) 102.4(3), C6-C5-C9 ) 105.8 (3), C7-C6-
C5 ) 104.4(3), C6-C7-C8 ) 103.6(4), C7-C8-C9 ) 103.8-
(4), C2-C9-C8 ) 113.9(3), C2-C9-C5 ) 104.4(3), C8-
C9-C5 ) 105.2(3), C4-O10-C11 ) 118.3(3).
alkynyl)carbene complex 1, it is thought that the second
equivalent of compound 6 would induce a transfer of
the S-acyl group from compound 8 to give cyclopentene-
1-thione complexes 9. The latter compounds are quite
stable, and all attempts to smoothly disengage the
sulfur ligand from the tungsten compounds 9, e.g. by
reaction with pyridine in THF, resulted in formation of
intractable product mixtures. The metal moiety of
compounds 9 must therefore be considered as a kind of
protecting group. While the chemistry of thioketones has
been extensively investigated,8 R,â-unsaturated thio-
ketones have been scarcely studied.9,10
Structural details of compound 9a were derived from
a crystal structure analysis (Figure 1). The W-S1-C2-
C3 backbone is almost planar, with a dihedral angle of
4.3(4)° and C2-S1-W angle of 115.7(1)°, and bisects
the angle between two neighboring carbonyl ligands,
C17-W-S1-C2 ) -44.1(2). On the basis of the sum of
C-C bond angles of the bridgehead carbon atoms of
320.2° for C5 (C4-C5-C6 ) 112.0(4)° + C4-C5-C9 )
102.4(3)° + C6-C5-C9 ) 105.8(3)°) and 323.5° for C9
(C2-C9-C8 ) 113.9(3)° + C2-C9-C5 ) 104.4(3)° +
C8-C9-C5 ) 105.2(3)°), both of which are smaller than
expected for an ideal tetrahedral configuration, the
a
Reaction time at 20 °C and molar ratio of compounds 1
b
and 6. Isolated yields of compounds 9 after chromatography
on silica gel.
acylates RC(dO)S-, thiol(NH-imino)acylates RC(dNH)S-,
and thiol(NPh-imino)acylates MeC(dNPh)S-, respec-
tively, with high regioselectivity and under mild condi-
tions.
Cyclop en ta d ien yl Th iola cyla te Com p lexes
Addition of thiocarboxylic acids 6a ,b to (1-alkynyl)-
carbene tungsten complexes 1a ,b in the presence of a
base, e.g. triethylamine, at 20 °C affords cyclopentene-
1-thione complexes 9a ,b (Scheme 2). Optimal yields
were obtained, if 2 equiv (instead of 1) of thiocarboxylic
acid was applied.
Even though intermediates of this reaction have not
been isolated, it can be reasonably assumed that 4-(thio-
carboxy)-1-tungsta-1,3,5-hexatrienes 7 are formed and
rapidly undergo π-cyclization to cyclopentadiene com-
plexes 8. Support of this hypothesis is provided by
related studies with nitrogen and phosphorus nucleo-
philes,6 as well as by a direct observation of compound
8b in solution by H and 13C NMR spectra. Compound
1
(8) For reviews see: (a) Voss, J . In Houben-Weyl, Methods of Organic
Chemistry; Georg Thieme Verlag: Stuttgart, Germany, 1985; Vol. E11,
pp 188-231. (b) Schaumann, E. In The Chemistry of Double-Bonded
Functional Groups; Patai, S., Ed.; Wiley: Chichester, U.K., 1999;
Chapter 17. (c) Metzner, P. Synthesis 1992, 1185-1199. (d) Molina,
M. T.; Yanez, M.; Mo, O.; Notario, R.; Abboud, J .-L. M. In The
Chemistry of Double-Bonded Functional Groups; Patai, S., Ed.;
Wiley: Chichester, U.K., 1997; Supplement A3, Chapter 23.
(9) (a) Valle´e, Y. Rev. Heteroat. Chem. 1993, 8, 1-20. (b) Pelloux-
Le´on, N. In Gas-Phase Reactions in Organic Synthesis; Valle´e, Y., Ed.;
Gordon and Breach: Amsterdam, 1997; Chapter 6.
8a , which is expected to be even less stable than
compound 8b for reasons of ring strain, could not be
detected by NMR spectra. While 1,3-dioxycyclopenta-
dienes 3 are very reactive and were found to rapidly
generate [2 + 2] cycloadducts with (1-alkynyl)carbene
complex 1a (Scheme 1),7 a corresponding [2 + 2]
cycloadduct has not been formed from sulfur compounds
8 (Scheme 2). On the basis of the fact that best yields
of the cyclopentene-1-thione complexes 9 are obtained
if 2 equiv of thiocarboxylic acids 6 is reacted with (1-
(10) (a) Metzner, B.; Vialle, J . Bull. Soc. Chim. Fr. 1972, 3138-
3145. (b) Metzner, B.; Vialle, J . Bull. Soc. Chim. Fr. 1973, 1317-1325.
(c) Metzner, B.; Vialle, J . Bull. Soc. Chim. Fr. 1973, 1703-1707. (d)
Metzner, P. Bull. Soc. Chim. Fr. 1973, 2297-2300.

Organic Syntheses via Transition Metal Complexes
Organometallics, Vol. 19, No. 12, 2000 2375
Sch em e 3. Th iol(NH-im in o)a cyla tes of
Tetr a h yd r op en ta len es, -in d en es, a n d -a zu len es 12,
Resp ectively, fr om NH-Th ioa m id es 10 a n d
(1-Alk yn yl)ca r ben e Com p lexes 1
Sch em e 4. F r a gm en ta tion of
Th iol(NH-im in o)a cyla tes 12
imino)acylates 12b-d ,f,g, containing six- and seven-
membered-ring systems, could be isolated by crystalli-
zation and even survived purification by flash chroma-
tography to an appreciable amount.
Compounds 12 were stable in the solid state, but in
solution at 50 °C (5 h) they underwent a smooth
fragmentation into compounds 9 and nitriles 13. This
transformation could be followed by NMR spectra.
The pathway suggested for the fragmentation of thiol-
(NH-imino)acylates 12 is assumed to involve a syn/ anti
isomerization of the CdN bond to give the isomer 12′,
which exhibits the stereochemistry required for frag-
mentation presumably to give the metal-free cyclopen-
tene-1-thione 14 and the nitrile complex (RCN)M(CO)5
15, from which compounds 9 and 13 are finally derived
by transmetalation (Scheme 4).
a
Chemical yields of compounds 12 at 20 °C (20 min), molar
b
Spectroscopic features characteristic of cyclopentene-
1-thione complexes 9 include the chemical shifts of the
bridgehead protons (e.g., 9a at δ 2.54 and 2.84 and 9b
at δ 2.47 and 2.51) as well as the corresponding carbon
atoms (e.g., 9a at δ 52.5 and 58.1 and 9b at δ 46.6 and
52.4) at relatively low field, which appears to be associ-
ated not only with the influence of the neighboring
π-systems but also with the angle strain induced by the
ring size (vide supra). A marked downfield shift is
observed also for the signals 2-H and C2 of cyclopentene-
1-thiones 9 (2-H at δ 6.35-6.49 and C2 at δ ca. 120)
compared to the cyclopentadienes 12 derived thereof
(2-H at δ 4.44-4.68 and C2 at δ ca. 100). In line with
expectation is the low-field shift of the carbon signals
of the CdS unit (e.g., 9a at δ 237.5 and 9b at 236.8) as
well as of the CdN moiety (e.g., 12b at δ 190.7 and 12c
at 191.8), which in each case is influenced by coordina-
tion to the M(CO)5 moiety.
ratio 1:1 of starting components 1 and 10. Chemical yields
of compounds 9 on thermal fragmentation of compounds 12.
hexahydropentalene skeleton is expected to be quite
strained. The distance C2-C3 ) 1.397(5) Å is much
shorter than expected for a C-C single bond, and is
similar to C3-C4 ) 1.360(5) Å, implying a strong
π-polarization with a positive charge centered at the
allyl unit C2-C3-C4 and a negative charge at W(CO)5
In line with this observation is the low-field shift of the
carbon atoms, e.g. compound 9a : C4, δ 195.0; C2 δ 121.5;
C2, δ 237.5.
-
.
Cyclop en ta d ien yl Th iol(NH-im in o)a cyla te
Com p lexes
Since cyclopentadiene derivatives 8 containing thio-
carboxylate substituents could not be isolated but
readily underwent solvolysis to cyclopentene-1-thione
complexes 9a ,b (Scheme 2), we prepared cyclopenta-
dienes 12 containing thiol(imino)acylate substituents,
which were assumed to be more stable toward solvolysis
than compounds 8. Cyclopentadiene thiol(NH-imino)-
acylate complexes 12b-d ,f,g were obtained in 82-95%
yields by addition of thioamides RC(dS)NH2 10 to (1-
alkynyl)carbene complexes 1 at 20 °C (20 min) (Scheme
3). Except for the tetrahydropentalene derivatives 12a,e,
which due to their inherent ring strain underwent a
spontaneous fragmentation to complexes 9a ,d by elimi-
nation of benzonitrile (13b), the (more stable) thiol(NH-
The tetrahydroindene compound 12b was character-
ized by a crystal structure analysis (Figure 2). The
unsaturated five-membered ring exhibits the expected
pattern of alternating bond distances: C2-C6 ) 1.333-
(4) Å, C2-C3 ) 1.469(4) Å, C3-C4 ) 1.341(4) Å, C4-
C5 ) 1.499(4) Å. The saturated six-membered ring
adopts a chair conformation. The W(CO)5 unit is at-
tached to the NH-iminium (not to the sulfur) atom of
the thiol(NH-iminium)acylate unit in an essentially
planar sickle-shape arrangement of the W1,N15,C14,-
S1,C2 backbone: W1-N15-C14-S1 ) -3.0(4)°, N15-

2376 Organometallics, Vol. 19, No. 12, 2000
Wu et al.
Sch em e 5. Th iol(NP h -im in o)a cyla tes of
Tetr a h yd r op en ta len es, -in d en es, a n d -a zu len es,
fr om NP h -Th ioa m id es 16 a n d (1-Alk yn yl)ca r ben e
Com p lexes 1
F igu r e 2. Molecular structure of tetrahydroindene com-
plex 12b. Selected bond lengths (Å) and angles (deg): W1-
N15 ) 2.227 (3), S-C14 ) 1.736(3), S1-C2 ) 1.765(3), C2-
C6 ) 1.333(4), C2-C3 ) 1.469(4), C3-C4 ) 1.341(4), C4-
O11 ) 1.353(3), C4-C5 ) 1.497(4), C5-C6 ) 1.499(4), C5-
C10 ) 1.528(4), C6-C7 ) 1.495(4), C7-C8 ) 1.523(5), C8-
C9 ) 1.519(5), C9-C10 ) 1.518(5), O10-C12 ) 1.433(4),
C12-C13 ) 1.491(4), C14-N15 ) 1.277(4), C14-C16 )
1.499(4); C14-S1-C2 ) 103.7(1), C6-C2-C3 ) 1.5(3),
C6-C2-S1 ) 125.2(2), C3-C2-S1 ) 123.3(2), C4-C3-
C2 ) 106.3(3), C3-C4-O11 ) 130.7(3), C3-C4-C5 )
111.5(3), O11-C4-C5 ) 117.8(3), C4-C5-C6 ) 102.3(2),
C4-C5-C10 ) 115.6(3), C6-C5-C10 ) 110.6(2), C2-C6-
C7 ) 131.5(3), C2-C6-C5 ) 108.5(3), C7-C6-C5 ) 119.4-
(3), C6-C7-C8 ) 108.6 (3), C9-C8-C7 ) 110.7(3), C10-
C9-C8 ) 111.3(3), C9-C10-C5 ) 109.4(3), C4-O11-C12
) 114.4(2), O11-C12-C13 ) 108.6(3), N15-C14-C16 )
122.5(3), N15-C14-S1 ) 117.4(2), C16-C14-S1 ) 120.2-
(2), C14-N15-W1 ) 135.0(2).
a
Chemical yields of compounds syn-17 at 20 °C (25 min),
b
molar ratio of starting components 1:10 ) 1:1. Molar ratio
of syn- and anti-17 after heating of syn-17 to 50 °C (20 min).
c Chemical yields of compounds 18, if reaction between com-
pounds 1 and 16 is performed in the presence of Et3N at 20
°C (20 min).
Interestingly, it was possible to generate compounds 18,
which are isomers of compounds 17, if the reaction
between (1-alkynyl)carbene complex 1 with the (N-
phenyl)thioacetamide 16 was performed in the presence
of triethylamine at 20 °C (20 min) (Scheme 5).
C14-S1-C2 ) -172.6(3)°, perpendicular to the cyclo-
pentadiene ring, C14-S1-C2-C3 ) -93.4(3)°.
The hexahydroazulene complex syn-18c was charac-
terized by a crystal structure analysis (Figure 3). The
unsaturated ring of the ligand exhibits the expected
pattern of alternating bond distances, C4-C5 ) 1.512-
(3) Å, C5-C6 ) 1.497(4) Å, C6-C7 ) 1.353(8) Å, C7-
C13 ) 1.471(3) Å, C4-C13 ) 1.350(4) Å. The seven-
membered ring adopts a chair conformation. The W(CO)5
unit is attached to the NH-iminium atom syn to the
sulfur atom in an essentially planar sickle-shaped
arrangement of the W1,N1,C2,S3,C4 backbone: W1-
N1-C2-S3 ) 8.6(3)°, N1-C2-S3-C4 ) -170.0(2),
almost perpendicular to the cyclopentadiene ring, C2-
S3-C4-C5 ) -85.3(2)°.
Cyclop en ta d ien yl Th iol(NP h -im in o)a cyla te
Com p lexes
Since cyclopentadiene derivates 12 are thermolabile
due to the presence of an NH functionality and undergo
fragmentation to cyclopentene-1-thione complexes 9
(Scheme 4), we generated thiol(NPh-imino)acylates 17,
which were anticipated to be more stable thermally.
Reaction of tungsten (1-alkynyl)carbene complexes with
(N-phenyl)thioacetamide (16) in diethyl ether at 20 °C
affords a yellow precipitate of the compounds syn-17
(Scheme 5). While the synthesis gave the compounds
syn-17 as a single stereoisomer, mixtures of syn- and
anti-17 were obtained from compounds syn-17 in ben-
zene at 50 °C. The mixture could not be separated by
chromatography on silica gel, probably due to an inter-
conversion of isomers under these conditions. Thus, the
mixture was analyzed by NMR spectra. The most
striking differences of chemical shifts of the correspond-
ing isomers include the signals of NdCCH3 (syn-17 at
δ 1.66 and anti-17b at δ 2.44) and ortho-H of C6H5 (syn-
17 at δ 6.44 and anti-17b at δ 6.84), as well as an NOE
enhancement between NdCCH3 and ortho-H of C6H5
for compound syn-17b, but not for anti-17b. It should
be noted that migration of the methine proton within
the cyclopentadiene ring was not observed at 50 °C.11
Experimental support of the assumption that 1-met-
alla-1,3,5-hexatrienes of type 7 (Scheme 2) would be
intermediates in these reactions is provided by the
isolation of thioenol esters 20 on addition of thiocar-
boxylic acids 6 to (1-alkynyl)carbene complex 19 (Scheme
6). The latter reaction follows a pattern similar to that
previously found for the addition of carboxylic acid to
compound 19.12 Other than 1-metalla-1,3,5-hexatrienes
7, compounds 20 do not undergo π-cyclization at 20 °C
and therefore could be isolated. They exhibit spectro-
scopic features, which are related to those of the
corresponding acyloxy derivatives, including the ex-
pected 13C and H NMR shift of crucial NMR signals;
e.g. 20a : WdC δ 312.2, SCdO δ 196.5, C2 δ 140.0,
OCH2 δ 72.9; 2-H δ 7.33, OCH2 δ 4.45; [(OC)5Wd
1
(11) (a) Pauli, A.; Meier, H. Chem. Ber. 1987, 120, 1617-1620. (b)
Aumann, R.; Go¨ttker-Schnetmann, I.; Fro¨hlich, R. Eur. J . Org. Chem.
1999, 2545-2561.
(12) Aumann, R.; J asper, B.; La¨ge, M.; Krebs, B. Organometallics
1994, 13, 3502-3509.

Organic Syntheses via Transition Metal Complexes
Organometallics, Vol. 19, No. 12, 2000 2377
analyses were determined on a Perkin-Elmer 240 elemental
analyzer. Analytical TLC plates, Merck DC-Alufolien Kiesegel
60F240, were viewed by UV light (254 nm) and stained by iodine.
Rf values refer to TLC tests. Chromatographic purifications
were performed on Merck Kieselgel 100. Pentacarbonyl[3-
(cyclopent-1-enyl)-1-ethoxy-2-propyn-1-ylidene]tungsten (1a )
and -chromium (1d ), pentacarbonyl[3-(cyclohex-1-enyl)-1-
ethoxy-2-propyn-1-ylidene]tungsten (1b) and -chromium (1e),
and pentacarbonyl[3-(cyclohept-1-enyl)-1-ethoxy-2-propyn-1-
ylidene]tungsten (1c) and -chromium (1f) were prepared
according to ref 6.
(a ) Rea ction of Th ioa cylic Acid s w ith (1-Alk yn yl)-
ca r b en e Com p lexes 1. (3a R*,6a S*)-P en t a ca r b on yl(3-
et h oxy-4,5,6,6a -t et r a h yd r o-3a H -p en t a len e-1-t h ion e-S)-
tu n gsten (9a ). A solution of pentacarbonyl[3-(cyclopent-1-
enyl)-1-ethoxy-2-propyn-1-ylidene)tungsten (1a ; 236 mg, 0.50
mmol) in 1 mL of n-hexane was added dropwise to a solution
of thioacetic acid (6a ; 76 mg, 1.00 mmol) in 1 mL of diethyl
ether/n-hexane (1:1) in the presence of triethylamine (40 mg,
0.40 mmol). The mixture was stirred for 2 h at 20 °C. Solvents
were removed in vacuo, and the residue was rapidly separated
by chromatography on silica gel (column 20 × 2 cm) with
n-pentane/dichloromethane (3:1) to give a red fraction of
compound 9a (385 mg, 76%; Rf ) 0.5 in n-pentane/diethyl ether
10:1, mp 76 °C). Reaction of compounds 1a and 6a in the molar
ratio 1:1 resulted in lower yields of compound 9a (ca. 48% after
4 h). Reaction of (1-alkynyl)carbene complex 1a with thioben-
zoic acid (6b) in the molar ratio 1:2 produced compound 9a in
73% yield:
F igu r e 3. Molecular structure of hexahydroazulene com-
plex syn-18c (code 1224.aum). Selected bond lengths (Å)
and bond angles (deg): W1-N1 ) 2.288(2), N1-C2 )
1.291(3), N1-C31 ) 1.455(3), C2-C21 ) 1.496(3), C2-S3
) 1.760(3), S3-C4 ) 1.752(3), C4-C13 ) 1.350(4), C4-
C5 ) 1.512(3), C5-C6 ) 1.497(4), C6-C7 ) 1.353(3), C7-
C13 ) 1.473(4), C7-C8 ) 1.491(4), C8-C9 ) 1.525(4), C9-
C10 ) 1.526(4), C10-C11 ) 1.525(5), C11-C12 ) 1.530(4),
C12-C13 ) 1.494(3); C2-N1-C31 ) 116.6(2), C2-N1-
W1 ) 129.9(2), C31-N1-W1 ) 113.5(2), N1-C2-C21 )
125.4(2), N1-C2-S3 ) 115.7(2), C21-C2-S3 ) 118.9(2),
C2-S3-C4 ) 107.2(1), C5-C4-C13 ) 110.1(2), S3-C4-
C13 ) 123.5(2), S3-C4-C5 ) 124.8(2), C4-C5-C6 )
101.2(2), C7-C6-O61 ) 123.0(2), C5-C6-C7 ) 111.9(2),
C5-C6-O61 ) 125.1(2), C6-C7-C13 ) 107.2(2), C6-C7-
C8 ) 127.7(2), C8-C7-C13 ) 125.1(2), C7-C8-C9 )
114.4(2), C8-C9-C10 ) 114.2(2), C9-C10-C11 ) 115.8-
(3), C10-C11-C12 ) 114.0(2), C11-C12-C13 ) 113.8(2),
C4-C13-C7 ) 109.6(2), C4-C13-C12 ) 127.9(2), C7-
C13-C12 ) 122.4(2).
Sch em e 6. Gen er a tion of
4-(S-Th ioa cyl)-1-tu n gsta -1,3-bu ta d ien es 20
1H NMR (C6D6): δ 6.29 (1 H, s, 2-H), 3.41 (OCH2), 2.84 and
2.54 (1 H each, m each, 3a- and 6a-H); 1.72 and 1.37, 1.35,
and 1.02 (1 H each, m each, diastereotopic 4-H2 and 6-H2), 1.11
and 0.90 (1 H each, m each, diastereotopic 5-H2), 0.80 (3 H, t,
OCH2CH3). 13C NMR (C6D6): δ 237.5 (Cq, CdS), 202.3 and
198.8 (Cq each, trans- and cis-CO of W(CO)5), 195.0 (Cq, C3),
121.5 (CH, C2), 69.9 (OCH2), 58.1 and 52.5 (CH each, C3a and
C6a), 33.0 and 28.3 (CH2 each, C4 and C6), 24.2 (CH2, C5),
14.0 (OCH2CH3). IR (diethyl ether; cm-1 (%)): 2067.3 (5),
1941.9 (100), 1912.2 (30) [ν(CtO)]. MS (70 eV; m/e 184W (%)):
506 (27) [M+], 422 (100) [M+ - 3 CO], 366 (40) [M+ - 5 CO].
Anal. Calcd for C15H14O6SW (506.2): C, 35.56; H, 2.77.
Found: C, 35.45; H, 2.76. X-ray crystal structure analysis of
compound 9a (code 1068.AUM): formula C15H14O6SW, M )
506.17, red crystals 0.40 × 0.25 × 0.20 mm, a ) 12.808(7) Å,
b ) 11.627(3) Å, c ) 11.886(1) Å, â ) 101.68(3)°, V ) 1733.4-
(11) Å3, Fcalcd ) 1.940 g cm-3, µ ) 68.09 cm-1, empirical
absorption correction via ψ scan data (0.172 e T e 0.343), Z
) 4, monoclinic, space group P21/c (No. 14), λ ) 0.710 73 Å, T
) 223 K, ω/2θ scans, 7161 reflections collected (+h,(k,(l), (sin
θ)/λ ) 0.62 Å-1, 3526 independent (Rint ) 0.055) and 2800
observed reflections (I g 2 σ(I)), 209 refined parameters, R1
) 0.023, wR2 ) 0.056, maximum residual electron density 0.89
(-1.67) e Å-3 close to tungsten, hydrogens calculated and
refined as riding atoms.13
a
Reaction time at 20 °C in a molar ratio of compounds 19
and 6. b Isolated yields of compounds 20 after chromatography
on silica gel.
C(OEt)CHdC(Ph)OCOMe:12 WdC δ 306.2, OCdO δ
166.5, C2 δ 132.4, OCH2 δ 80.2; 2-H δ 7.78, OCH2
δ
4.50].
(3a R*,7a S*)-P en ta ca r bon yl[th ioa cetic a cid (3-eth oxy-
4,5,6,7-tetr a h yd r o-3a H-in d en -1-yl) ester -S]tu n gsten (8b)
a n d (3a R*,7a S*)-P en t a ca r b on yl(3-et h oxy-3a ,4,5,6,7,7a -
h exa h yd r oin d en e-3-th ion e-S)tu n gsten (9b). Pentacarbo-
nyl[3-(cyclohex-1-enyl)-1-ethoxy-2-propyn-1-ylidene]tungsten
(1b; 243 mg, 0.50 mmol) was reacted with thiobenzoic acid (6b;
138 mg, 1.00 mmol) in diethyl ether/n-pentane (1:1) as
described above for 6 h at 20 °C. Chromatography on silica
Exp er im en ta l Section
All operations were carried out in an atmosphere of argon.
1
All solvents were dried and distilled prior to use. All H and
13C NMR spectra were routinely recorded on Bruker ARX 300
and AM 360 instruments. IR spectra were recorded on a Biorad
Digilab Division FTS-45 FT-IR spectrophotometer. Elemental

2378 Organometallics, Vol. 19, No. 12, 2000
Wu et al.
gel (column 20 × 2 cm) afforded a red fraction of compound
9b (179 mg, 69%, Rf ) 0.6 in n-pentane/diethyl ether 10:1, mp
95 °C). Reaction of compound 1b with thioacetic acid (6a ) in a
molar ratio of 1:2 gave compound 9b in 71% yield, while the
reaction in a 1:1 molar ratio afforded only a 39% yield. The
NMR spectrum in [D6]benzene of a solution of compound 1b
and thioacetic acid (6a ) in a molar ratio of 1:2 in the presence
of 0.5 equiv of Et3N after 2 h at 20 °C shows signals of
compound 8b as the major product.
12b.
1
8b. H NMR (C6D6): δ 4.98 (1 H, s, 2-H), 3.56 (OCH2), 1.74
(3H, s, CH3), 2.55-0.86 (9 H, m), 1.06 (3 H, t, OCH2CH3). 13C
NMR (C6D6): δ 202.0 and 198.5 [Cq each, trans- and cis-CO of
W(CO)5], 195.3 (Cq, CdO), 162.1 (Cq, C3), 141.4 (Cq, C1), 96.1
(CH, C2), 64.9 (OCH2), 49.2 (CH, C3a), 30.1 (CH3); 28.1, 24.6,
and 20.5 (1:1:2, C4-C7), 13.7 (OCH2CH3).
1H NMR (C6D6): δ 7.69 (1 H, s, NH), 4.65 (1 H, s, 2-H), 3.45
(2 H, m, OCH2), 2.45 (1 H, dd, 3a-H), 2.22 and 0.77 (1 H each,
m each, diastereotopic 7-H2); 2.62 and 1.67, 1.58 and 0.81, 1.40,
and 0.95 (1 H each, m each, diastereotopic 4-H2-6-H2), 1.39
(3 H, s, CH3), 1.08 (3 H, t, OCH2CH3). 13C NMR (C6D6): δ 202.6
and 198.6 [Cq each, trans- and cis-CO of W(CO)5], 190.7 (Cq,
CdN), 168.5 (Cq, C3), 147.8 (Cq, C1), 120.2 (Cq, C7a), 100.5
(CH, C2), 65.6 (OCH2), 51.6 (CH, C3a), 28.7 (CH3), 31.1 (CH2,
C7), 28.0 (CH2, C4), 26.4 and 24.8 (CH2 each, C5 and C6), 14.3
(OCH2CH3). IR (diethyl ether; cm-1 (%)): 2067.4 (5), 1931.1
(100), 1902.6 (30) [ν(CtO)]. MS (70 eV; m/e 184W (%)): 561 (8)
[M+], 520 (18) [M+ - CH3CN], 477 (11) [M+ - 3 CO], 421 (10)
[M+ - 5 CO]. Anal. Calcd for C18H19O6NSW (561.3): C, 38.50;
H, 3.38; N, 2.49. Found: C, 38.31; H, 3.37; N 2.09. X-ray crystal
structure analysis of compound 12b (code 1196.AUM): formula
9b.
1H NMR (C6D6): δ 6.35 (1 H, s, 2-H), 3.52 (OCH2), 2.47 and
2.51 (1 H each, 3a-H and 7a-H), 1.66 and 1.52, 1.36, and 1.20
(1 H each, m each, diastereotopic 4-H2 and 7-H2), 1.1-1.01 (4
H, m, 5-H2 and 6-H2), 0.89 (3 H, t, OCH2CH3). 13C NMR
(C6D6): δ 236.8 (Cq, CdS), 202.0 and 198.5 [Cq each, trans-
and cis-CO of W(CO)5], 195.8 (Cq, C3), 119.2 (CH, C2), 69.5
(OCH2), 52.4 and 46.6 (CH each, C3a and C7a), 28.1 and 24.6
(CH2 each, C4 and C7), 20.5 (2 CH2, C5 and C6), 13.7
(OCH2CH3). IR (diethyl ether; cm-1 (%)): 2067.3 (5), 1941.1
(100), 1912.5 (30) [ν(CtO)]. MS (70 eV; m/e 184W (%)): 520
(33) [M+], 464 (68) [M+ - 2 CO], 436 (48) [M+ - 3 CO], 408
(42) [M+ - 4 CO], 380 (27) [M+ - 5 CO].
(b) Rea ction s of Th ioa cylim in o Acid s 10 w ith (1-
Alk yn yl)ca r ben e Com p lexes 1. P en ta ca r bon yl(3-eth oxy-
4,5,6,6a -tetr a h yd r o-3a H-p en ta len e-1-th ion e-S)tu n gsten
(9a ). A solution of pentacarbonyl[3-(cyclopent-1-enyl)-1-ethoxy-
2-propyn-1-ylidene]tungsten (1a ; 236 mg, 0.50 mmol) in 1 mL
of n-hexane was added dropwise to a solution of thiobenzamide
(10a ; 69 mg, 0.50 mmol) in 1 mL of diethyl ether/n-hexane
(1:1). A color change from brown to red was observed within
20 min at 20 °C, after which time the starting material was
consumed completely according to TLC. Compound 9a was
obtained in 92% yield after chromatography on silica gel (vide
supra).
(3a R*)-P en ta ca r bon yl[th ioa cetim id ic a cid (3-eth oxy-
4,5,6,7-tetr ah ydr o-3a H-in den -1-yl) ester -N]tu n gsten (12b)
a n d P en ta ca r bon yl(3-eth oxy-3a ,4,5,6,7,7a -h exa h yd r oin -
d en e-1-th ion e-S)tu n gsten (9b). Pentacarbonyl[3-(cyclohex-
1-enyl)-1-ethoxy-2-propyn-1-ylidene]tungsten (1b; 243 mg, 0.50
mmol) was reacted with thioacetamide (10; 38 mg, 0.50 mmol)
as described above to give compound 12b (255 mg, 91%, Rf )
0.5 in n-pentane/diethyl ether 10:1, mp 108 °C). Compound
12b can be purified by fast chromatography on silica gel, but
partial decomposition must be allowed in this case. Compound
12b undergoes a smooth fragmentation into compound 9b (vide
supra) in 92% yield and acetonitrile (13a ) (identified by MS
and 13C NMR) in dichloromethane at 50 °C, 5 h.
C
18H19NO6SW, M ) 561.25, yellow-orange crystal 0.15 × 0.10
× 0.05 mm, a ) 7.355(1) Å, b ) 27.384(1) Å, c ) 10.663(1) Å,
â ) 108.46(1)°, V ) 2037.1(3) Å3, Fcalcd ) 1.830 g cm-3, µ )
58.05 cm-1, empirical absorption correction via SORTAV (0.476
e T e 0.760), Z ) 4, monoclinic, space group P21/n (No. 14), λ
) 0.710 73 Å, T ) 198 K, ω and æ scans, 8286 reflections
collected ((h, (k, (l), (sin θ)/λ ) 0.65 Å-1, 4672 independent
(Rint ) 0.022) and 4126 observed reflections (I g 2σ(I)), 250
refined parameters, R1 ) 0.024, wR2 ) 0.053, maximum
residual electron density 0.78 (-1.65) e Å-3 close to tungsten,
hydrogens calculated and refined as riding atoms.13
P en ta ca r bon yl[th ioben zim id ic a cid (3-eth oxy-4,5,6,7-
tetr a h yd r o-3a H-in d en -1-yl) ester -N]tu n gsten (12c) a n d
P en ta ca r bon yl(3-eth oxy-3a ,4,5,6,7,7a -h exa h yd r oin d en e-
1-th ion e-S)tu n gsten (9b). A mixture of pentacarbonyl[3-
(cyclohex-1-enyl)-1-ethoxy-2-propyn-1-ylidene]tungsten (1b; 243
mg, 0.50 mmol) and thiobenzamide (10b; 69 mg, 0.50 mmol)
in a 2 mL screw-top vessel in 2 mL of diethyl ether was stirred
for 20 min to give a yellow solution. The solvent was replaced
by n-pentane, from which compound 12c was obtained at -15
°C (293 mg, 94%, Rf ) 0.5 in n-pentane/diethyl ether 10:1,
yellow crystals, mp 114 °C). Compound 12c undergoes a
smooth fragmentation into compound 9b (vide supra) in 94%
yield and benzonitrile (13b) (identified by MS and 13C NMR)
in dichloromethane at 50 °C (5 h).
12c. 1H NMR (C6D6): δ 8.29 (1 H, s, NH); 6.87, 6.76, and
6.60 (1:2:2 H, Ph), 4.44 (1 H, s, 2-H), 3.28 (2 H, m, OCH2, 2.20
(1 H, dd, 3a-H), 2.01 and 0.70 (1 H each, m each, diastereotopic
7-H2); 2.57 and 1.63, 1.54 and 0.83, 1.34 and 0.90 (1 H each,
m each, diastereotopic 4-H2-6-H2), 0.93 (3 H, t, OCH2CH3).
13C NMR (C6D6): δ 202.8 and 198.6 [Cq each, trans- and cis-
CO of W(CO)5], 191.8 (Cq, CdN), 167.6 (Cq, C3), 145.5 (Cq, C1),
137.5 (Cq, i-C Ph); 130.6, 128.1, and 127.2 (1:2:2, Ph), 120.1
(Cq, C7a), 100.5 (CH, C2), 65.3 (OCH2), 51.3 (CH, C3a), 30.5
(CH2, C7), 28.0 (CH2, C4), 26.4 and 24.7 (CH2 each, C5 and
C6), 14.2 (OCH2CH3). IR (diethyl ether; cm-1 (%)): 2067.0 (5),
1931.5 (100), 1902.0 (30) [ν(CtO)]. MS (70 eV; m/e 184W (%)):
623 (1) [M+], 511 (6) [M+ - 4 CO]. Anal. Calcd for C23H21NO6-
SW (623.3): C, 44.28; H, 3.37; N 2.25. Found: C, 44.19; H,
3.49; N, 2.04.
(13) Data sets were collected with Nonius MACH3 and KappaCCD
diffractometers, equipped with a Nonius FR591 rotating anode genera-
tor. Programs used: data collection EXPRESS (Nonius BV, 1994) and
COLLECT (Nonius BV, 1998), data reduction MolEN (K. Fair, Enraf-
Nonius BV, 1990) and Denzo-SMN (Otwinowski, Z.; Minor, W. Methods
Enzymol. 1997, 276, 307-326), absorption correction for CCD data
SORTAV (Blessing, R. H. Acta Crystallogr. 1995, A51, 33-37. Blessing,
R. H. J . Appl. Crystallogr. 1997, 30, 421-426), structure solution
SHELXS-97 (Sheldrick, G. M. Acta Crystallogr. 1990, A46, 467-473),
structure refinement SHELXL-97 (Sheldrick, G. M. Universita¨t Go¨t-
tingen, 1997), graphics DIAMOND (Brandenburg, K. Universita¨t Bonn,
1997).
1
13b. H NMR (C6D6): δ 7.02, 6.90, and 6.73 (2:1:2 H, Ph).
13C NMR (C6D6): δ 132.2, 131.9, and 128.9 (CH each, 1:2:2,
Ph), 118.7 (Cq, CN).
(3a R*)-P en ta ca r bon yl[th ioa cetim id ic a cid (3-eth oxy-
4,5,6,7,8-p en ta h yd r o-3a H-a zu len -1-yl) ester -N]tu n gsten
(12d ) a n d (3a R*,8a S*)-P en ta ca r bon yl(3-eth oxy-4,5,6,7,8,-

Organic Syntheses via Transition Metal Complexes
Organometallics, Vol. 19, No. 12, 2000 2379
8a-h exah ydr o-3aH-azu len e-1-th ion e-S)tu n gsten (9c). Pen-
tacarbonyl[3-(cyclohept-1-enyl)-1-ethoxy-2-propyn-1-ylidene]-
tungsten (1c; 250 mg, 0.50 mmol) was reacted with thioacet-
amide (10a ; 38 mg, 0.50 mmol) as described above to give
compound 12d (273 mg, 95%, Rf ) 0.4 in n-pentane/dichloro-
methane 3:1, mp 63 °C). Thermolysis of compound 12d in
dichloromethane to 50 °C (5 h) gave thione complex 9c (90%,
red crystals from diethyl ether/n-pentane, mp 82 °C, Rf ) 0.7
in n-pentane/dichloromethane 3:1) and acetonitrile (13b)
(identified by its 13C NMR and MS).
(OCH2), 58.9 and 52.0 (CH each, C3a and C6a), 33.3 and 28.3
(CH2 each, C4 and C6), 24.1 (CH2, C5), 14.0 (OCH2CH3). IR
(diethyl ether; cm-1 (%)): 2061.2 (5), 1939.6 (100), 1916.1 (30)
[ν(CtO)]. MS (70 eV; m/e (%)): 374 (9) [M+], 262 (13) [M+ - 4
CO], 234 (100) [M+ - 5 CO]. Anal. Calcd for C15H14O6SCr
(374.3): C, 48.13; H, 3.74. Found: C, 47.51; H, 3.86.
(3a R*)-P en ta ca r bon yl[th ioben zim id ic a cid (3-eth oxy-
4,5,6,7-tetr ah ydr o-3aH-in den -1-yl) ester -N]ch r om iu m (12f)
a n d (3a R*,7a S*)-P en t a ca r b on yl(3-et h oxy-3a ,4,5,6,7,7a -
h exa h yd r oin d en e-1-th ion e-S)ch r om iu m (9e). Pentacar-
bonyl[3-(cyclohex-1-enyl)-1-ethoxy-2-propyn-1-ylidene]chromi-
um (1e; 178 mg, 0.50 mmol) was reacted with thiobenzamide
(10b; 69 mg, 0.50 mmol) as decribed above to give compound
12f (201 mg, 82%, Rf ) 0.5 in n-pentane/diethyl ether 10:1,
yellow crystals, mp 118 °C). Thermolysis of compound 12f (98
mg, 0.20 mmol) in dichloromethane at 50 °C, 5 h and
subsequent chromatograpgy on silica gel with n-pentane/
diethyl ether (10:1) gave compound 9e (73 mg, 95%, Rf ) 0.7
in n-pentane/diethyl ether 10:1, red crystals, mp 107 °C).
12f.
12d .
1H NMR (C6D6): δ 7.85 (1 H, s, NH), 4.64 (1 H, s, 2-H), 3.45
(2 H, m, OCH2), 2.74 (1 H, dd, 3a-H), 1.51 and 0.99 (1 H each,
m each, diastereotopic 8-H2); 2.24 and 2.08, 1.02 and 1.53, 1.21
and 1.38, 1.39 and 1.38 (1 H each, m each, diastereotopic 4-H2-
7-H2), 1.44 (3 H, s, CH3), 1.09 (3 H, t, OCH2CH3). 13C NMR
(C6D6): δ 202.6 and 198.5 [Cq each, trans- and cis-CO of
W(CO)5], 190.4 (Cq, CdN), 166.8 (Cq, C3), 150.9 (Cq, C1), 122.8
(Cq, C8a), 100.3 (CH, C2), 65.6 (OCH2), 54.9 (CH, C3a), 30.8
(CH2, C8); 29.9, 29.4, 29.3, and 27.2 (CH2 each, C4-C7), 27.9
(CH3), 14.4 (OCH2CH3). IR (diethyl ether; cm-1 (%)): 2067.6
(5), 1931.9 (100), 1902.3 (30) [ν(CtO)]. MS (70 eV; m/e 184W
(%)): 575 (4) [M+], 491 (6) [M+ - 3 CO], 435 (6) [M+ - 5 CO].
Anal. Calcd for C19H21NO6SW (575.3): C, 39.65; H, 3.65; N,
2.43. Found: C, 39.45; H, 3.71; N, 2.25.
1H NMR (C6D6): δ 8.62 (1 H, s, NH), 7.11-6.36 (5 H, Ph), 4.88
(1 H, s, 2-H), 3.55 (2 H, broad, OCH2), 2.21 and 0.78 (1 H each,
m each, diastereotopic 7-H2), 2.60 and 1.67, 1.58 and 0.81, 1.41
and 0.97 (1 H each, m each, diastereotopic 4-H2-6-H2), 1.10
(3 H, broad, OCH2CH3). 13C NMR (C6D6): δ 221.3 and 214.8
[Cq each, trans- and cis-CO of Cr(CO)5], 195.5 (Cq, CdN), 170.4
(Cq, C3), 152.2 (Cq, C1), 138.0 (Cq, i-C Ph), 131.5, 129.1, and
127.7 (CH each, 1:2:2, Ph), 117.1 (Cq, C7a), 98.3 (CH, C2), 66.0
(OCH2), 52.3 (CH, C3a), 30.3 (CH2, C7); 29.5, 26.7, and 24.7
(CH2 each, C4-C6), 14.3 (OCH2CH3). IR (diethyl ether; cm-1
(%)): 2060.5 (5), 1929.6 (100), 1906.2 (30) [ν(CtO)]. MS (70
eV; m/e (%)): 491 (9) [M+], 388 (14) [M+ - PhCN], 379 (24)
9c.
[M+ - 4 CO], 351 (18) [M+ - 5 CO]. Anal. Calcd for C23H21
-
NO6SCr (491.5): C, 56.16; H, 4.27; N, 2.85. Found: C, 56.06;
1H NMR (C6D6): δ 6.49 (1 H, s, 2-H), 3.50 (OCH2), 2.50 and
2.35 (1 H each, m each, 3a-H and 8a-H); 1.53 and 1.39, 1.40
and 1.26 (1 H, m each, diastereotopic 4-H2 and 8-H2); 1.27 and
1.04, 1.24 and 1.02, 1.12 and 0.99 (1 H, m each, diastereotopic
5-H2-7-H2), 0.83 (3 H, t, OCH2CH3). 13C NMR (C6D6): δ 236.2
(Cq, CdS), 202.0 and 198.5 [Cq each, trans- and cis-CO of
W(CO)5], 194.9 (Cq, C3), 120.6 (CH, C2), 69.3 (OCH2), 57.5 and
52.2 (CH each, C3a and C8a), 31.8 and 30.9 (CH2 each, C4
and C8); 28.1, 27.8, and 27.4 (CH2 each, C5-C7), 13.7
(OCH2CH3). IR (diethyl ether; cm-1 (%)): 2067.1 (5), 1941.3
(100), 1912.6 (30) [ν(CtO)]. MS (70 eV; m/e 184W (%)): 534
(31) [M+], 478 (56) [M+ - 2 CO], 394 (19) [M+ - 5 CO]. Anal.
Calcd for C17H18O6SW (534.4): C, 38.17; H, 3.37. Found: C,
38.13; H, 3.38.
(3a R*,8a S*)-P en ta ca r bon yl(3-eth oxy-4,5,6,6a -tetr a h y-
d r o-3a H-p en ta len e-1-th ion e-S)ch r om iu m (9d ). Pentacar-
bonyl[3-(cyclopent-1-enyl)-1-ethoxy-2-propyn-1-ylidene]chro-
mium (1d; 170 mg, 0.50 mmol) was reacted with thiobenzamide
(10b; 69 mg, 0.50 mmol) as described above in diethyl ether
at 20 °C (20 min). Chromatography with n-pentane/dichlo-
romethane (3:1) gave compound 9d (163 mg, 87%, Rf ) 0.6 in
n-pentane/diethyl ether 10:1, mp 70 °C, red crystals from
diethyl ether/n-pentane). 1H NMR (C6D6): δ 6.30 (1 H, s, 2-H),
3.43 (3-OCH2), 2.88 and 2.58 (1 H each, m each, 3a-H and 6a-
H); 1.71 and 1.41, 1.44, and 1.11 (1 H each, m each, diaste-
reotopic 4-H2 and 6-H2), 1.16 and 0.94 (1 H each, m each,
diastereotopic 5-H2), 0.84 (3 H, t, OCH2CH3). 13C NMR
(C6D6): δ 239.7 (Cq, CdS), 223.8 and 216.8 [Cq each, trans-
and cis-CO of Cr(CO)5], 194.9 (Cq, C3), 119.3 (CH, C2), 69.6
H, 4.22; N, 3.11.
9e.
1H NMR (C6D6): δ 6.38 (1 H, s, 2-H), 3.44 (OCH2), 2.45 and
2.25 (1 H each, m each, 3a-H and 7a-H), 1.66 and 1.56, 1.35
and 1.27 (1 H each, m each, diastereotopic 4-H2 and 7-H2); 1.08
(4 H, m, 5-H2 and 6-H2), 0.81 (3 H, t, OCH2CH3). 13C NMR
(C6D6): δ 239.1 (Cq, CdS), 223.9 and 217.2 [Cq each, trans-
and cis-CO of Cr(CO)5], 195.8 (Cq, C3), 117.0 (CH, C2), 69.4
(OCH2), 53.8 and 46.4 (CH each, C3a and C7a), 28.5 and 25.0
(CH2 each, C4 and C7), 20.8 and 20.9 (CH2 each, C5 and C6),
14.0 (OCH2CH3). IR (diethyl ether; cm-1 (%)): 2061.8 (5),
1939.6 (100), 1916.2 (30) [ν(CtO)]. MS (70 eV; m/e (%)): 388
(7) [M+], 276 (13) [M+ - 4 CO], 248 (80) [M+ - 5 CO]. Anal.
Calcd for C16H16O6SCr (388.4): C, 49.44; H, 4.12. Found: C,
49.12; H, 3.93.
P en ta ca r bon yl[th ioa cetim id ic a cid (3-eth oxy-4,5,6,7,8-
p en ta h yd r o-3a H-a zu len -1-yl) ester -N]ch r om iu m (12g)
a n d P en ta ca r bon yl(3-eth oxy-4,5,6,7,8,8a -h exa h yd r o-3a H-
a zu len e-1-th ion e-S)ch r om iu m (9f). Pentacarbonyl[3-(cy-
clohept-1-enyl)-1-ethoxy-2-propyn-1-ylidene]chromium (1f; 184
mg, 0.50 mmol) was reacted with thioacetamide (10a ; 38 mg,
0.50 mmol) to give compound 12g (199 mg, 90%, Rf ) 0.4 in

2380 Organometallics, Vol. 19, No. 12, 2000
Wu et al.
n-pentane/diethyl ether 1:10, yellow crystals, mp 69 °C).
Thermolysis of compound 12g (98 mg, 0.20 mmol) in dichloro-
methane at 50 °C (5 h) and subsequent chromatography on
silica gel with n-pentane/diethyl ether 10:1 affords compound
9f (76 mg, 95%, Rf ) 0.7 in n-pentane/diethyl ether 10:1, red
crystals, mp 85 °C).
ester -N]tu n gsten (18b). Pentacarbonyl[3-(cyclohex-1-enyl)-
1-ethoxy-2-propyn-1-ylidene]tungsten (1b; 243 mg, 0.50 mmol)
was reacted with (N-phenyl)thioacetamide (16; 76 mg, 0.50
mmol) in diethyl ether at 20 °C (25 min). A yellow precipitate
was produced, collected by centrifugation, washed two times
with n-pentane, and dried in vacuo (15 Torr, 20 °C) to give
almost clean compound syn-17b (305 mg, 96%, Rf ) 0.3 in
n-pentane/dichloromethane 3:1, mp 110 °C). Compound syn-
17b was transformed into a 2:1 mixture of syn- and anti-17b
in benzene at 50 °C after 3 h, which could not be separated by
chromatography on silica gel, since they exist in dynamic
equilibrium, but were analyzed instead as mixtures by NMR
spectra at 600 MHz. Reaction of compounds 1b and 16 in the
presence of 1 equiv of triethylamine at 20 °C (20 min) afforded
compound 18b (264 mg, 83%, Rf ) 0.3 in n-pentane/diethyl
ether 10:1, mp 106 °C).
12g. 1H NMR (C6D6): δ 7.37 (1 H, s, NH), 4.66 (1 H, s, 2-H),
3.47 (2 H, m, OCH2), 2.75 (1 H, dd, 3a-H), 1.53 and 0.90 (1 H
each, m each, diastereotopic 8-H2); 2.29 and 2.07, 1.53 and 1.02,
1.36 and 1.20, 1.34 and 1.32 (1 H each, m each, diastereotopic
4-H2-7-H2), 1.45 (3 H, s, CH3), 1.10 (3 H, t, OCH2CH3). 13C
NMR (C6D6): δ 221.4 and 215.4 [Cq each, trans- and cis-CO of
Cr(CO)5], 190.7 (Cq, CdN), 166.7 (Cq, C3), 150.6 (Cq, C1), 122.8
(Cq, C8a), 100.4 (CH, C2), 65.5 (OCH2), 54.8 (CH, C3a), 30.8
(CH2, C8); 29.9, 29.4, 29.3, and 27.2 (CH2 each, C4-C7), 28.7
(SCCH3), 14.4 (OCH2CH3). IR (diethyl ether; cm-1 (%)): 2062.5
(5), 1930.6 (100), 1906.8 (30) [ν(CtO)]. MS (70 eV; m/e (%)):
443 (4) [M+], 359 (5) [M+ - 3 CO], 303 (8) [M+ - 5 CO]. Anal.
Calcd for C19H21NO6SCr (443.4): C, 51.46; H, 4.77; N, 3.16.
Found: C, 51.51; H, 5.01; N, 2.93.
syn-17b (anti-17b).
1
9f. H NMR (C6D6): δ 6.49 (1 H, s, 2-H), 3.53 (OCH2), 2.54
and 2.41 (1 H each, m each, 3a-H and 8a-H); 1.55 and 1.38,
1.40 and 1.25 (1 H, m each, diastereotopic 4-H2 and 8-H2); 1.27
and 1.04, 1.23 and 1.02, 1.12 and 0.98 (1 H each, m each,
diastereotopic 5-H2-7-H2), 0.88 (3 H, t, OCH2CH3). 13C NMR
(C6D6): δ 238.4 (Cq, CdS), 223.6 and 216.9 [Cq each, trans-
and cis-CO of Cr(CO)5], 195.2 (Cq, C3), 118.0 (CH, C2), 69.1
(OCH2), 58.6 and 51.8 (CH each, C3a and C8a), 32.0 and 30.9
(CH2 each, C4 and C8); 28.2, 27.8, and 27.4 (CH2 each, C5-
C7), 13.7 (OCH2CH3). IR (diethyl ether; cm-1 (%)): 2061.3 (5),
1939.7 (100), 1616.0 (30) [ν(CtO)]. MS (70 eV; m/e (%)): 402
(25) [M+], 346 (56) [M+ - 2 CO], 262 (19) [M+ - 5 CO]. Anal.
Calcd for C17H18O6SCr (402.4): C, 50.70; H, 4.47. Found: C,
50.54; H, 4.57.
P en tacar bon yl[N-ph en yl-th ioacetim idic acid (3-eth oxy-
2,4,5,6-tetr a h yd r op en ta len -1-yl) ester -N]tu n gsten (18a ).
Pentacarbonyl[3-(cyclopent-1-enyl)-1-ethoxy-2-propyn-1-ylidene]-
tungsten (1a ; 236 mg, 0.50 mmol) was reacted with (N-phenyl)-
thioacetamide (16; 76 mg, 0.50 mmol) in 2 mL of dichloro-
methane in the presence of 1 equiv of triethylamine with
stirring at 20 °C (20 min). Fast chromatography on silica gel
afforded yellow compound 18a (277 mg, 89%, Rf ) 0. 4 in
n-pentane/diethyl ether 10:1, mp 92 °C).
1H NMR (600 MHz, C6D6): δ 6.99, 6.80, and 6.46 (7.11, 6.87,
and 6.85) (2:1:2 m-, p-, and o-H Ph), 4.85 (4.69) (1 H, s, 2-H),
3.46 (3.46) (2 H, m, OCH2), 2.47 (2.45) (1 H, dd, 3a-H), 2.84
(2.50) (1 H, m), 2.22 (2.22) (1 H, m), 1.71 (1.77) (1 H, m), 1.66
(2.54) (3 H, s, NdCCH3), 1.63 (1.66) (1 H, m), 1.41 (1.53) (1 H,
m), 0.89 (0.79) (3 H, m), 1.08 (1.07) (3 H, t, OCH2CH3). 13C
NMR (C6D6): δ 203.8 and 199.6 (203.2 and 199.2) [Cq each,
trans- and cis-CO of W(CO)5], 187.5 (185.0) (Cq, CdN), 168.8
(168.7) (Cq, C3), 155.3 (155.2) (Cq, i-C Ph), 148.1 (147.5) (Cq,
C1); 129.4, 126.3, and 121.0 (129.6, 126.9, and 121.0) (2:1:2
m-, p-, and o-C Ph), 121.4 (121.5) [Cq, C7a], 100.3 (100.2) (CH,
C2), 65.6 (65.6) (OCH2), 51.7 (51.2) (CH, C3a); 31.1, 28.7, 26.6,
and 24.8 (31.0, 28.6, 26.3, and 24.7) (CH2 each, C4-C7), 22.2
(29.7) (NdCCH3), 14.3 (14.4) (OCH2CH3). IR (diethyl ether;
cm-1 (%)): 2061.3 (5), 1931.7 (100), 1901.8 (30) [ν(CtO)]. MS
(70 eV; m/e 184W (%)): 637 (14) [M+], 525 (47) [M+ - 4 CO],
497 (55) [M+ - 5 CO]. Anal. Calcd for C24H23NO6SW (637.4):
C, 45.21; H, 3.61; N, 2.20. Found: C, 45.28; H, 3.68; N, 1.86.
18b.
18a .
1H NMR (400 MHz, C6D6): δ 6.99, 6.79, and 6.42 (2:1:2, m-,
p-, o-H Ph), 3.65 (2 H, m, OCH2), 3.13 (2 H, s, 2-H2), 2.17 and
1.80 (4:2, m each, 4-H2-6-H2), 1.50 (s, 3 H, CH3), 1.04 (3 H, t,
OCH2CH3). 13C NMR (400 MHz, C6D6): δ 203.9 and 199.6 [Cq
each, trans- and cis-CO of W(CO)5], 189.9 (Cq, CdN), 170.2
(Cq, C3), 158.2 (Cq, C1), 155.5 (Cq, i-C Ph), 129.9, 126.1, and
121.1 (2:1:2, m-, p-, o-C Ph), 124.1 and 102.5 (Cq each, C3a
and C6a), 65.9 (OCH2), 49.9 (CH2, C2); 30.1, 26.2, and 25.9
(CH2 each, C4-C7), 21.6 (NdCCH3), 15.1 (OCH2CH3). IR
(diethyl ether; cm-1 (%)): 2067.1 (5), 1932.0 (100), 1901.2 (30)
[ν(CtO)]. MS (70 eV; m/e 184W (%)): 539 (0.3) [M+ - 3 CO],
483 (0.4) [M+ - 5 CO], 299 (5) [M+ - W(CO)5], 118 (100). Anal.
Calcd for C23H21NO6SW (623.3): C, 44.32; H, 3.40; N, 2.25.
Found: C, 44.32; H, 3.59; N, 1.70.
1H NMR (400 MHz, C6D6): δ 6.99, 6.79, and 6.47 (2:1:2, m-,
p-, o-H Ph), 3.38 (2 H, m, 3-OCH2), 2.60 (2 H, s, 2-CH2), 2.27
and 1.31 (4:2, m each, 4-H-7-H), 1.42 (s, 3 H, CH3), 1.02 (3 H,
t, 3-OCH2CH3). 13C NMR (C6D6): δ 203.9 and 199.7 [Cq each,
trans- and cis-CO of W(CO)5], 189.4 (Cq, CdN), 162.0 (Cq, C3),
158.9 (Cq, C1), 155.5 (Cq, i-C Ph); 129.4, 126.2, and 121.1 (2:
1:2, m-, p-, o-C Ph), 116.4 and 107.0 (Cq each, C3a and C7a),
65.8 (OCH2), 42.0 (CH2, C2), 25.8 and 22.9 (2:2, C4-C7), 21.7
(NdCCH3), 15.2 (OCH2CH3). IR (diethyl ether; cm-1 (%)):
2066.9 (5), 1932.2 (100), 1902.0 (30) [ν(CtO)]. MS (70 eV; m/e
184W (%): 553 (1) [M+ - 3 CO], 497 (3) [M+ - 5 CO], 313 (5)
[M+ - W(CO)5], 118 (100). Anal. Calcd for C24H23NO6SW
(637.4): C, 45.23; H, 3.64; N, 2.20. Found: C, 44.46; H, 3.43;
N, 1.96.
P en tacar bon yl[N-ph en ylth ioacetim idic acid (3-eth oxy-
4,5,6,7-tetr a h yd r o-3a H-in d en -1-yl) ester -N]tu n gsten (syn -
17b a n d a n ti-17b) a n d P en ta ca r bon yl[N-p h en ylth ioa ce-
tim id ic a cid (3-eth oxy-4,5,6,7-tetr a h yd r o-3a H-in d en -1-yl)
P en tacar bon yl[N-ph en ylth ioacetim idic acid (3-eth oxy-
4,5,6,7,8-p en ta h yd r o-3a H-a zu len -1-yl) ester -N]tu n gsten
(syn -17c a n d a n ti-17c) a n d P en ta ca r bon yl[N-p h en ylth io-

Organic Syntheses via Transition Metal Complexes
Organometallics, Vol. 19, No. 12, 2000 2381
a cetim id ic a cid (3-eth oxy-4,5,6,7,8-p en ta h yd r o-3a H-a zu -
len -1-yl) ester -N]tu n gsten (18c). Pentacarbonyl[3-(cyclohept-
1-enyl)-1-ethoxy-2-propyn-1-ylidene]tungsten (1c; 250 mg, 0.50
mmol) and (N-phenyl)thioacetamide (16; 76 mg, 0.50 mmol)
was reacted as described above in diethyl ether at 20 °C (25
min) to give compound syn-17c (305 mg, 94%, Rf ) 0.5 in
n-pentane/dichloromethane 3:1, yellow crystals, mp 108 °C).
Compound syn-17c was heated in benzene at 50 °C (3 h) to
give a 4:5-mixture of syn- and anti-17c. The reaction of
compounds 1c and 16 in diethyl ether in the presence of 1
equiv of triethylamine at 20 °C (20 min) afforded compound
18c (280 mg, 86%, Rf ) 0.4 in n-pentane/diethyl ether 10:1,
yellow crystals, mp 102 °C).
and 5511 observed reflections (I g 2σ(I)), 309 refined param-
eters, R1 ) 0.022, wR2 ) 0.053, maximum residual electron
density 1.34 (-1.07) e Å-3close to tungsten, hydrogens calcu-
lated and refined as riding atoms.13
P en t a ca r b on yl[3-(S-t h ioa cet yl)-1-et h oxy-3-p h en yl-2-
p r op en -1-ylid en e]tu n gsten (20a ). Pentacarbonyl(3-phenyl-
1-ethoxy-2-propyn-1-ylidene)tungsten (19; 241 mg, 0.50 mmol)
in 1 mL of n-hexane was added dropwise to a solution of
thioacetic acid (6a ; 38 mg, 0.50 mmol) and triethylamine (40
mg, 0.40 mmol) in 1 mL of diethyl ether. The mixture was
stirred for 3 h at 20 °C and separated by rapid chromatography
on silica gel (column 20 × 2 cm) with n-pentane/dichloro-
methane (5:1) to give a brown fraction containing compound
20a (198 mg, 71%, Rf ) 0.4 in dichloromethane/n-pentane 1:3,
mp 82 °C).
syn-17c (anti-17c).
20a .
1H NMR (C6D6): δ 7.33 (1 H, s, 2-H); 7.56, 7.10, and 7.05 (2:
1:2, Ph), 4.45 (2 H, q, OCH2), 1.72 (3 H, s, COCH3), 1.14 (3 H,
t, OCH2CH3). 13C NMR (C6D6): δ 312.2 (WdC), 203.6 and 197.3
[Cq each, trans- and cis-CO of W(CO)5], 196.5 (3-SCO), 149.3
(Cq, C3), 142.8 (Cq, i-C Ph), 140.0 (CH, C2), 129.4, 128.8, and
127.9 (2:1:2, CH each, Ph), 79.2 (OCH2), 29.9 (COCH3), 14.5
(OCH2CH3). IR (diethyl ether; cm-1 (%)): 2068.0 (10), 1976.3
(5), 1947.0 (100) [ν(CtO)]. MS (70 eV; m/e 184W (%)): 558 (2)
[M+], 446 (3) [M+ - 4 CO], 418 (7) [M+ - 5 CO]. Anal. Calcd
for C18H14O7SW (558.2): C, 38.69; H, 2.51. Found C, 38.45; H,
2.47.
P en ta ca r bon yl[3-(S-th ioben zoyl)-1-eth oxy-3-p h en yl-2-
p r op en -ylid en e]tu n gsten (20b). Pentacarbonyl(3-phenyl-1-
ethoxy-2-propyn-1-ylidene)tungsten (19; 241 mg, 0.50 mmol)
was reacted with thiobenzoic acid (6b; 69 mg, 0.50 mmol) as
described above in diethyl ether/n-hexane (1:1) for 6 h at 20
°C. Fast chromatography on silica gel (column 20 × 2 cm) with
n-pentane/dichloromethane (5:1) gave compound 20b (211 mg,
68%, Rf ) 0.3 in dichloromethane/n-pentane 1:3, brown solid).
20b.
1H NMR (600 MHz, C6D6): δ 7.01, 6.81, and 6.50 (7.12, 6.88,
and 6.83) (2:1:2 m-, p-, and o-H Ph), 4.82 (4.68) (1 H, s, 2-H),
3.45 (3.46) (2 H, m, OCH2), 2.78 (2.44) (1 H, dd, 3a-H), 2.45
(2.38) (2 H, m), 2.08 (2.28) (1 H, m), 1.65 (2.54) (3 H, s, SCCH3),
1.51 (1.51) (3 H, m), 1.27 (1.27) (2 H, m), 1.07 (1.07) (2 H, m),
1.07 (1.07) (3 H, t, OCH2CH3). 13C NMR (C6D6): δ 203.8 and
199.6 (203.0 and 199.3) [Cq each, trans- and cis-CO of W(CO)5],
187.2 (184.6) (Cq, CdN), 167.1 (16.47) (Cq, C3), 155.4 (155.3)
(Cq, i-C Ph), 151.1 (149.6) (Cq, C1); 129.4, 126.3, and 121.0
(129.3, 127.0, and 121.4) (2:1:2 m-, p-, and o-C Ph), 124.3
(123.7) [Cq, C8a], 100.2 (101.9) (CH, C2), 65.6 (65.6) (OCH2),
55.0 (54.9) (CH, C3a); 30.9, 29.8, 29.7, 29.2, and 27.3 (30.7,
29.4, 29.3, 28.5, and 27.1) (CH2 each, C4-C7), 22.1 (21.5)
(CH3), 14.3 (15.1) (OCH2CH3). IR (diethyl ether; cm-1 (%)):
2068.3 (5), 1931.1 (100), 1901.8 (30) [ν(CtO)]. MS (70 eV; m/e
184W (%)): 651 (0.25) [M+], 567 (2) [M+ - 3 CO], 511 (5) [M+
-
5 CO]. Anal. Calcd for C25H25NO6SW (651.4): C, 46.08; H, 3.84;
N, 2.15. Found: C, 45.98; H, 3.89; N, 2.02.
18c.
1H NMR (C6D6): δ 7.50 (1 H, s, 2-H); 7.82, 7.00, and 6.92 (2:
1:2, m each, 3-thiobenzoyl); 7.56, 7.09, and 7.06 (2:1:2, 3-Ph),
4.45 (2 H, q, OCH2), 1.06 (3 H, t, OCH2CH3). 13C NMR (C6D6):
δ 310.9 (WdC), 204.2 and 197.3 [Cq each, trans- and cis-CO of
W(CO)5], 195.8 (CdO), 150.3 (Cq, C3), 143.0 and 136.7 (i-C
each, Ph each), 140.1 (CH, C2), 133.8, 128.9, and 127.8 (1:2:2,
CH each, 3-thiobenzoyl), 129.4, 128.8, and 128.0 (2:1:2, CH
each, 3-Ph), 78.6 (OCH2), 13.8 (OCH2CH3). IR (diethyl ether;
cm-1 (%)): 2068.4 (10), 1975.4 (5), 1947.4 (100) [ν(CtO)]. MS
(70 eV; m/e 184W (%)): 620 (2) [M+], 536 (3) [M+ - 3 CO], 508
(4) [M+ - 4 CO]. Anal. Calcd for C23H16O7SW (620.3): C, 44.49;
H, 2.58. Found C, 44.35; H, 2.65.
1H NMR (C6D6): δ 7.01, 6.81, and 6.48 (2:1:2, m-, p-, o-H Ph),
3.37 (2 H, m, OCH2), 2.66 (2 H, s, 2-H2); 2.47, 2.33, and 1.42
(2:2:6, m each, 4-H-8-H), 1,47 (s, 3 H, CH3), 1.03 (3 H, t,
OCH2CH3). 13C NMR (C6D6): δ 203.9 and 199.7 [Cq each, trans-
and cis-CO of W(CO)5], 189.4 (Cq, CdN), 163.9 (Cq, C3), 161.3
(Cq, C1), 155.6 (Cq, C-i Ph), 129.5, 126.2, and 121.1 (2:1:2, m-,
p-, o-C Ph), 122.8 and 108.4 (Cq each, C3a and C8a), 65.8
(OCH2), 42.1 (CH2, C2), 32.6, 30.1, 29.8, 28.6, and 24.9 (CH2
each, C4-C7), 21.5 (NdCCH3), 15.2 (OCH2CH3). IR (diethyl
ether; cm-1 (%)): 2067.0 (5), 1932.0 (100), 1902.5 (30) [ν(Ct
O)]. MS (70 eV; m/e 184W (%)): 567 (2) [M+ - 3 CO], 511 (10)
[M+ - 5 CO]. X-ray crystal structure analysis of compound
syn-18c (code 1224.AUM: formula C25H25NO6SW, M ) 651.37,
yellow crystal 0.35 × 0.30 × 0.15 mm, a ) 8.757(1) Å, b )
10.516(1) Å, c ) 14.976(1) Å, R ) 74.03(1)°, â ) 79.35(1)°, γ )
75.46(1)°, V ) 1273.5(2) Å3, Fcalcd ) 1.699 g cm-3, µ ) 46.57
cm-1, empirical absorption correction via SORTAV (0.293 e
T e 0.542), Z ) 2, triclinic, space group P1h (No. 2), λ ) 0.710 73
Å, T ) 198 K, ω and æ scans, 8586 reflections collected ((h,
(k, (l), (sin θ)/λ ) 0.65 Å-1, 5820 independent (Rint ) 0.025)
Ack n ow led gm en t. This work was supported by the
Deutsche Forschungsgemeinschaft and the Fonds der
Chemischen Industrie. E.W. and P.S. thank the Finnish
Academy for financial support.
Su p p or tin g In for m a tion Ava ila ble: Details of the X-ray
crystal structure analyses. This material is available free of
charge via the Internet at http://pubs.acs.org.
OM000107V