Syntheses, spectroscopy and fluxional behavior of the η3-crotyl, C3H4(CH3), pyrolidinyldithiocarbamate molybdenum complexes

Article abstract of DOI:10.1016/S0020-1693(03)00045-8

The endo- and exo-complexes [Mo{η³-C₃H₄(CH₃)}(η ²-S₂CNC₄H₈)(CO)(η ²-diphos)] (diphos: dppm={bis(diphenylphosphino)methane} (2); dppe={1,2-bis(diphenylphosphino)ethane} (3) are prepared by reacting the 16-electron complex [Mo{η³-C₃H₄(CH₃)}(η ²-S₂CNC₄H₈)(CO)₂] (1) with diphos in refluxing acetonitrile. The orientations of endo and exo are defined in such a way that the open face of the allyl group and carbonyl group are in the same direction in the former and in the opposite direction in the latter. The variable temperature ¹H NMR was used to confirm that there was no allyl rotation behavior of endo?exo interconversion of 2 before the thermal decomposition. X-ray crystal structure of exo-2 has been employed to elucidate the exo orientation and the methyl moiety of the allyl ligand is found to orient away from the dppm ligand.

Full text of DOI:10.1016/S0020-1693(03)00045-8

Inorganica Chimica Acta 348 (2003) 271ꢁ278
/
www.elsevier.com/locate/ica
Note
Syntheses, spectroscopy and fluxional behavior of the h3-crotyl,
C3H4(CH3), pyrolidinyldithiocarbamate molybdenum complexes:
crystal structure of exo-[Mo{h3-C3H4(CH3)}(h2-
S2CNC4H8)(CO)(h2-dppm)]
Kuang-Hway Yih a,*, Gene-Hsiang Lee b, Shou-Ling Huang b, Yu Wang c
a Department of Applied Cosmetology, Hung Kuang University, 34 Chung Chi Road, Shalu, Taichung Hsien, Taiwan 433
b Instrumentation Center, College of Science, National Taiwan University, Taipei, Taiwan 106
c Department of Chemistry, National Taiwan University, Taipei, Taiwan 106
Received 14 October 2002; accepted 27 November 2002
Abstract
The endo- and exo-complexes [Mo{h3-C3H4(CH3)}(h2-S2CNC4H8)(CO)(h2-diphos)] (diphos: dppmꢀ
/
{bis(diphenylphosphi-
no)methane} (2); dppeꢀ
{1,2-bis(diphenylphosphino)ethane} (3) are prepared by reacting the 16-electron complex [Mo{h3-
/
C3H4(CH3)}(h2-S2CNC4H8)(CO)2] (1) with diphos in refluxing acetonitrile. The orientations of endo and exo are defined in such a
way that the open face of the allyl group and carbonyl group are in the same direction in the former and in the opposite direction in
the latter. The variable temperature 1H NMR was used to confirm that there was no allyl rotation behavior of endo l
/
exo
interconversion of 2 before the thermal decomposition. X-ray crystal structure of exo-2 has been employed to elucidate the exo
orientation and the methyl moiety of the allyl ligand is found to orient away from the dppm ligand.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Endo-, exo-orientations; h3-Crotyl molybdenum complexes; Pyrolidinyldithiocarbamate ligand; Crystal structures
1. Introduction
S2)X]. Recently, we reported the reactions of [Mo(h3-
allyl)(CO)2(h2-S2)X] (S2ꢀ
Et2NCS2, C4H8NCS2; S2ꢀ
(EtO)2PS2, XꢀCH3CN) with diphos (diphosꢀdppm,
/
/
The X-ray crystallographic studies [1] and fluxionality
[2] of the complexes with [Mo(h3-allyl)(CO)2(L2)X] (L2:
pyrazolylborate, b-diketonate, dithiocarbamate, X: neu-
tral monodentate ligand; L2: diphos, pyridylphosphane,
X: halide) have so far revealed three different solid-state
/
/
dppe, dppa) to produce the conformational endo-, exo-
complexes [Mo(h3-C3H5)(h2-S2)(CO)(h2-diphos)] [3]
and investigated the rotational behavior of allyl group
in these complexes. We have studied the relation of the
diphos ligands, the ratios, and free allyl rotational
energy of the endo-, exo-complexes showed the dppe
ligand improves the formation of the endo-[Mo(h3-
C3H5){h2-S2P(OEt)2}(CO)(h2-dppe)] as the sole pro-
duct [4].
As an extension of our recent work on the stereo-
selective formation of the sole conformer, we employ
crotyl, C3H4(CH3), to investigate the dependence of the
ratio and interconversion of the endo- and exo-con-
formers.
structures as depicted in Fig. 1(Aꢁ
the intramolecular trigonal twist (Aꢁ
rotation of the triangular face formed by the L2X groups
is relative to the face formed by the allyl and the two
carbonyl groups. Only a few studies have been focused
on the derivatives of complexes [Mo(h3-allyl)(CO)(h2-
/
C) and attributed to
/B), in which the
* Corresponding author. Fax: ꢂ
E-mail address: khyih@sunrise.hkc.edu.tw (K.-H. Yih).
/
886-4-2632-10-46.
0020-1693/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0020-1693(03)00045-8

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K.-H. Yih et al. / Inorganica Chimica Acta 348 (2003) 271ꢁ278
/
singlet resonances at d 229.9 and 231.4 are attributed to
two chemically non-equivalent carbonyl groups and the
relative up-field singlet resonance at d 202.0 is assigned
to the carbon atom of the CS2 of the C4H8NCS2 ligand.
2.2. Synthesis of endo- and exo-(carbonyl)(h3-
crotyl)(h2-diphos)(h2-pyrolidinyldithiocarbamate)-
molybdenum(II) complex [Mo{h3-C3H4(CH3)}(h2-
S2CNC4H8)(CO)(h2-dppm)] (2) and [Mo{h3-
C3H4(CH3)}(h2-S2CNC4H8)(CO)(h2-dppe)] (3)
Fig. 1. Three possible structures A,
C3H5)(CO)2(L2)X].
B and C
for [Mo(h3-
2. Result and discussion
2.1. Synthesis of (h3-crotyl)(dicarbonyl)(h2-
pyrolidinyldithiocarbamate)molybdenum(II) complex
The reactions of complexes [Mo(h3-allyl)(CO)2-
(dithio)L] with phenanthroline, phenylacetylene [6] and
diphos [3] have been reported. Thus, treatment of
[Mo{h3-C3H4(CH3)}(h2-S2CNC4H8)(CO)2] (1) with
dppm or dppe in refluxing acetonitrile yields mixtures
of endo-, exo-[Mo{h3-C3H4(CH3)}(h2-S2CNC4H8)-
(CO)(h2-dppm)] (2) with endo:exo ratios of 1:20 or
endo-, exo-[Mo{h3-C3H4(CH3)}(h2-S2CNC4H8)(CO)-
(h2-dppe)] (3) with endo:exo ratios of 2:1 (Scheme 1).
[Mo{h3-C3H4(CH3)}(h2-S2CNC4H8)(CO)2] (1)
Treatment of [Mo(CH3CN)2{h3-C3H4(CH3)}(CO)2-
Br] with NH4(S2CNC4H8) in MeOH at room tempera-
ture resulted in a replacement reaction, affording the 16-
electron complex [Mo{h3-C3H4(CH3)}(h2-S2CNC4H8)-
(CO)2] (1) with 88% isolation yield. Preparation of the
16-electron complexes [Mo(h3-allyl)(CO)2(h2-S2CNR)]
from the reactions of [Mo(CH3CN)2(h3-allyl)(CO)2Br]
The air-stable yellowꢁorange compounds 2 and 3 are
/
soluble in dichloromethane and in acetonitrile and
insoluble in diethyl ether and in n-hexane. The orienta-
tions of endo and exo are defined to the open face of the
allyl group and carbonyl group in the same direction in
the former and in the opposite directions in the latter.
The spectroscopic and analytical data of 2 and 3 are
obtained. In the FAB mass spectra, base peaks with the
typical Mo isotope distribution are in good agreement
with NaS2CNR (RꢀC4H8, Et2) have been reported by
/
Shiu et al. [5]. The air-sensitive yellow compound 1 is
soluble in polar solvents and insoluble in n-hexane and
diethyl ether. Complex 1 is more soluble and air-
sensitive than the non-methylated complex [Mo(h3-
C3H5)(h2-S2CNC4H8)(CO)2]. The analytical data of 1
are in agreement with the formulation. FAB mass
spectrum of 1 shows a parent peak with the typical
Mo isotope distribution corresponding to the [Mꢂ]
molecular mass. The IR spectrum of 1 shows two
carbonyl-stretchings with equal intensity, indicating
that the two carbonyls are mutually cis. Due to the
with the [Mꢂ ꢁ
CO] molecular masses of 2 and 3. The IR
/
spectra of 2 and 3 show one terminal carbonyl-stretch-
ing band at 1770 and 1790 cmꢃ1, respectively, although
both isomers are known to be present in different ratios.
The mixtures of endo, exo-2 or endo, exo-3 are able to
1
methyl moiety, the room temperature H NMR spec-
distinguish from different 31P{1H}ꢁ31P{1H} coupling
/
trum of 1 exhibits five sets of resonances of the
C3H4(CH3) ligand which is typical of the ABCDX spin
patterns of unsymmetrical h3-allyl metal complexes.
Only one resonance of the Hsyn has been observed in
1H NMR spectra, which the methyl group occupies the
syn position of the allyl group (Scheme 1). In the
13C{1H} NMR spectrum of 1, three singlet resonances
appear in the carbonyl region. Two relative down-field
constants. The 31P{1H} NMR spectrum of 2 shows endo
2
resonances at d 9.7 and 36.1 (with J(PP)ꢀ
/
52.1 Hz)
2
and exo resonances at d 5.0 and 30.0 (with J(PP)ꢀ
60.7 Hz). Compared to the 31P{1H} NMR spectrum and
the structure of the complex [Mo(h3-C3H5)(CO)(h2-
S2CNC4H8)(h2-dppm)] [3], the resonances appear in
relative up-field with large coupling constant is assigned
to the exo-orientation and in the relative down-field
/
Scheme 1.

K.-H. Yih et al. / Inorganica Chimica Acta 348 (2003) 271ꢁ
/278
273
with small coupling constant is assigned to the endo-
orientation. Because of the different ratios of endo:exo-2
3.12 ppm, which is overlapped by one proton of the
NCH2 moiety of the dithiocarbamate ligand. Two
resonances are shown at the lowest field in the
13C{1H} NMR spectrum of 2, the relative down-field
triplet resonance is attributed to the carbon atom of the
carbonyl group that is coupled by two phosphorus
atoms and the relative up-field singlet resonance is
attributed to the CS2 of the dithiocarbamate ligand.
1
(1:20), the H and 13C{1H} NMR spectra of the major
product exo-2 can be assigned unambiguously from the
1
1Hꢁ1
/
H COSY and Hꢁ13
/
C COSY experiments. From
Fig. 2, the two Hanti protons appear at d 2.29 (d,
2J(HH)ꢀ11.7 Hz) and 2.35 (dd, 2J(HH)ꢀ
6.93 Hz,
3J(PH)ꢀ
19.2 Hz) and the Hsyn proton appears at d
/
/
/
Fig. 2. 1Hꢁ1
/
H COSY and 1Hꢁ13
C COSY NMR observations of the mixtures endo- and exo-2 in CDCl3.
/

274
K.-H. Yih et al. / Inorganica Chimica Acta 348 (2003) 271ꢁ278
/
Compared to the ratios of endo-, exo-[Mo{h3-
C3H4(CH3)}(h2-S2CNC4H8)(CO)(h2-dppm)] (2) (1:20),
endo-,
exo-[Mo(h3-C3H5)(h2-S2CNC4H8)(CO)(h2-
dppm)] (1:4) and endo-, exo-[Mo{h3-C3H4(CH3)}(h2-
S2CNC4H8)(CO)(h2-dppe)] (3) (2:1) and endo-, exo-
[Mo(h3-C3H5)(h2-S2CNC4H8)(CO)(h2-dppe)] (6:1), it is
clear that the stereoselective formation of the exo-
product by the methyl moiety of the allyl ligand is
improved.
1
2.3. Variable temperature H and 31P{1H} NMR
experiments of endo- and exo-complex 2
1
Variable temperature H NMR experiments can be
used to study the fluxional behavior of non-rigid
complexes. For example, the rearrangement involving
a pꢁ
and intramolecular trigonal twist behavior of complexes
[M(h3-C3H5)(CO)2(diphos)I] [8] (Mꢀ
Mo, W; diphosꢀ
/
s ꢁp [7] process of complexes [Tp?Mo(CO)2(allyl)]
/
/
/
Fig. 3. An ORTEP drawing with 50% thermal ellipsoids and atom-
numbering scheme for the complex exo-[Mo{h3-C3H4(CH3)}(h2-
S2CNC4H8)(CO)(h2-dppm)] (2).
dppm, dppe). Recently, we have described the allyl
rotational behavior of complexes [Mo(h3-C3H5)(h2-
S2CNC4H8)(CO)(h2-diphos)] (diphosꢀ
/dppm, dppe).
Thus, in order to investigate the fluxionality of the
crotyl complex endo-, exo-2, the variable temperature
1H and 31P{1H} NMR spectra were recorded in the
while the other is trans to carbonyl: S(2)Ã
/
MoÃ
/
C(1),
169.11(12)8. The SÃ
/
MoÃS angle of 68.958(17)8 in 2 is
/
similar to 68.459(17)8 in complex exo-[Mo(h3-C3H5)(h2-
range of 298ꢁ
/
328 K. In the range of 298ꢁ
318 K, the 1H
/
S2CNC4H8)(CO)(h2-dppm)] within the experimental
and 31P{1H} NMR spectra are not changed and the
ratio is retained. Surprisingly, the 31P{1H} NMR
spectra show only one resonance at d 10.2 ppm (Section
errors. The MoÃ
/
C(2), C(3) and C(4) bond distances
˚
are 2.329(4), 2.337(4) and 2.404(4) A, respectively. The
˚
S(1) distance of 2.5324(10) A (trans to phosphorus)
MoÃ
/
1
4, spectrum A) and the H NMR spectra show organic
˚
S(2) of 2.6197(10) A (trans
is clearly shorter than MoÃ
/
alkene resonances at d 4.8ꢁ5.8 at 323 K. From the
/
to CO) because of the greater trans effect induced by the
CO group than the diphos ligand.
The bond distances and intercarbon angle of allyl
above description, it is clear that the crotyl group breaks
away from the metal complex. The decomposition may
be due to the steric hindrance of the crotyl group in the
allyl rotational process. Formation of the endo-, exo-2 is
believed to proceed via one of the phosphorus coordina-
tion at the axial position trans to the crotyl ligand of 1
to afford a six coordination complex, followed by the
crotyl rotation to form the endo and exo orientations
and then the other phosphorus replace the carbonyl
group to form the endo- and exo-2.
˚
group in exo-2 (1.393(6), 1.393(6) A and 120.5(4)8) are
in the range of related MoII-allylic compounds (1.31ꢁ
/
˚
1.42 A, 115ꢁ1258) [9]. Selected bond distances and
/
angles for exo-[Mo{h3-C3H4(CH3)}(h2-S2CNC4H8)-
(CO)(h2-dppm)] (2) and exo-[Mo(h3-C3H5)(h2-S2CN-
C4H8)(CO)(h2-dppm)] are listed in Table 3. From this
˚
C1 bond distance of 2.404(4) A in exo-2
table, the MoÃ
/
˚
is significantly longer than that of 2.339(2) A in the non-
methylated allyl complex exo-[Mo(h3-C3H5)(h2-
S2CNC4H8)(CO)(h2-dppm)] due to the steric hindrance
of the methyl moiety.
2.4. X-ray structure determination of exo-[Mo{h3-
C3H4(CH3)}(h2-S2CNC4H8)(CO)(h2-dppm)] (2)
In order to confirm the orientation of the methyl
group, we have performed an X-ray diffraction study of
2 at 150 K. The ORTEP plot of 2 is shown in Fig. 3. In the
structure, the coordination geometry around the mo-
lybdenum atom is approximately an octahedron with
the two sulfur atoms, two phosphorus atoms, carbonyl
and the crotyl group occupying the six coordination
sites. The structure confirms an unequivalent allyl group
and the methyl moiety of the allyl ligand is oriented
toward CO group. One of the sulfur atoms of dithio
2.5. Conclusion
We employ two diphos ligands and crotyl ligand to
investigate the dependence of the ratios and interconver-
sion of the endo- and exo-conformers. The dppm ligand
improves the formation of exo-product, whereas the
dppe ligand improves the formation of endo-product.
The exo-complexes show large J(PP) coupling constant
than the endo-complexes. The resonances of dppm
complex appear in relative up-field for the exo-orienta-
ligand is trans to the diphos: S(1)Ã
/
MoÃP(2), 143.93(4)8,
/

K.-H. Yih et al. / Inorganica Chimica Acta 348 (2003) 271ꢁ
/278
275
tion and dppe complex appear in the relative up-field for
the endo-orientation. Steric effect of the crotyl ligand
improves the formation of exo-products and does not
CH3), 24.7 (s, NCH2CH2), 50.2 (s, NCH2), 55.0, 73.5 (s,
CH2), 77.0 (s, ÄCH), 202.0 (s, NCS2), 229.9, 231.4 (s,
CO). MS (FAB, NBA, m/z) 355 (Mꢂ), 327 (Mꢂ ꢁ
CO),
299 (Mꢂ ꢁ
2CO). Anal. Calc. for C11H15NO2S2Mo: C,
37.39; H, 4.28; N, 3.97%. Found: C, 37.42; H, 4.40; N,
3.88%.
Ä
/
/
/
induce allyl endo l
/
exo interconversion of 2 before the
/
thermal decomposition.
3. Experimental
3.3. Endo-, exo-(carbonyl)(h3-crotyl)(h2-diphos)(h2-
pyrolidinyldithiocarbamate)molybdenum(II) complex
[Mo{h3-C3H4(CH3)}(h2-S2CNC4H8)(CO)(h2-dppm)]
(2)
3.1. Materials
All manipulations were performed under nitrogen
using vacuum-line, drybox, and standard Schlenk tech-
niques. NMR spectra were recorded on an AM-300 or
an AM-500 WB FT-NMR spectrometer and are re-
ported in units of parts per million with residual protons
in the solvent as an internal standard (CDCl3, d 7.24).
IR spectra were measured on a Nicolate Avator-320
instrument and referenced to polystyrene standard,
using cells equipped with calcium fluoride windows.
MS spectra were recorded on a JEOL SX-102A spectro-
meter. Solvents were dried and deoxygenated by reflux-
ing over the appropriate reagents before use. n-Hexane,
diethyl ether, THF and benzene were distilled from
sodium-benzophenone. Acetonitrile and dichloro-
methane were distilled from calcium hydride, and
methanol was distilled from magnesium. All other
solvents and reagents were of reagent grade and used
as received. Elemental analyses and X-ray diffraction
studies were carried out at the Regional Center of
Analytical Instrument located at the National Taiwan
University. Mo(CO)6 and C3H4(CH3)Br were purchased
from Strem Chemical, C4H8NCS2NH4, dppm, and dppe
were purchased from Merck.
MeCN (20 ml) was added to a flask (100-ml) contain-
ing dppm (0.384 g, 1.0 mmol) and [Mo{h3-
C3H4(CH3)}(h2-S2CNC4H8)(CO)2] (1) (0.353 g, 1.0
mmol). The solution was refluxed for 1 h, and an IR
spectrum indicated completion of the reaction. After
removal of the solvent in vacuo, the residue was
redissolved with CH2Cl2 (10 ml). n-Hexane (15 ml)
was added to the solution and a yellowꢁ
endo-, exo-2 were formed which were isolated by
filtration (G4), washed with n-hexane (2ꢄ10 ml) and
/orange solids
/
subsequently drying under vacuum yielding endo-, exo-
[Mo{h3-C3H4(CH3)}(h2-S2CNC4H8)(CO)(h2-dppm)]
(2) (0.62 g, 87%). Further purification was accomplished
by recrystallization from 1/10 CH2Cl2/n-hexane. Spec-
troscopic data of endo-, exo-2 are as follows. IR (KBr,
cmꢃ1): n(CO) 1770(vs). MS (FAB, NBA, m/z) 721.5
(Mꢂ ꢁ
CO). Anal. Calc. for C35H37NOP2S2Mo: C,
/
59.23; H, 5.26; N, 1.97%. Found: C, 59.56; H, 5.10; N,
1.84%. 31P{1H} NMR (202 MHz, CDCl3, 298 K): endo-
2: d 9.7, 36.1 (d, 2J(PP)ꢀ
/
52.1 Hz, dppm). exo-2: d 5.0,
60.7 Hz, dppm). exo-2: 1H NMR (500
MHz, CDCl3, 298 K): d 1.60, 1.75, 1.77, 1.78 (m, 4H,
30.0 (d, 2J(PP)ꢀ
/
4
NCH2CH2), 2.26 (d, J(HH)ꢀ5.60 Hz, 3H, CH3), 2.29
/
3.2. (h3-Crotyl)(dicarbonyl)(h2-
(d, J(HH)ꢀ
6.93 Hz, 3J(PH)ꢀ
3.44 (m, 4H, NCH2), 3.12 (br, 1H, Hsyn), 4.01 (dt,
/
11.7 Hz, 1H, Hanti), 2.35 (dd, J(HH)ꢀ
/
3
3
pyrolidinyldithiocarbamate)molybdenum(II) complex
[Mo{h3-C3H4(CH3)}(h2-S2CNC4H8)(CO)2] (1)
/
19.2 Hz, 1H, Hanti), 2.68, 3.12, 3.26,
2
2J(HH)ꢀ
(dd, J(HH)ꢀ
/
15.1 Hz, J(PH)ꢀ
/
9.0 Hz, 1H, PCH2), 4.26
8.4 Hz, 1H, PCH2),
2
2
MeOH (20 ml) was added to a flask (100-ml) contain-
ing NH4S2CNC4H8 (0.164 g, 1.0 mmol) and
[Mo(CH3CN)2{h3-C3H4(CH3)}(CO)2Br] (0.370 g, 1.0
mmol). The solution was stirred for 5 min at room
/
15.1 Hz, J(PH)ꢀ
/
4.70 (m, 1H, Hc). 13C{1H} NMR (125 MHz, CDCl3,
298 K): d 20.0 (s, CH3), 24.5, 24.9 (s, NCH2CH2), 42.9
(t, J(PC)ꢀ19.4 Hz, PCH2), 48.7, 49.5 (s, NCH2), 51.9
/
2
2
temperature, and a yellowꢁ
which were isolated by filtration (G4), washed with n-
10 ml) and subsequently drying under
/orange solids 1 were formed
(d, J(PC)ꢀ
Hz, CH2ÄCH), 102.5 (s, CH2Ä
204.8 (s, CS2), 228.3 (t, J(PC)ꢀ
/
15.1 Hz, CHCH3), 87.6 (d, J(PC)ꢀ
CH), 126.3ꢁ134.5 (Ph),
12.6 Hz, CO).
/
9.6
/
/
/
2
hexane (2ꢄ
/
/
vacuum yielding [Mo{h3-C3H4(CH3)}(h2-S2CNC4H8)-
(CO)2] (1) (0.31 g, 88%). Further purification was
accomplished by recrystallization from 1/10 CH2Cl2/n-
hexane. Spectroscopic data of 1 are as follows. IR (KBr,
3.4. Endo-, exo-(carbonyl)(h3-crotyl)(h2-diphos)(h2-
pyrolidinyldithiocarbamate)molybdenum(II) complex
[Mo{h3-C3H4(CH3)}(h2-S2CNC4H8)(CO)(h2-dppe)]
(3)
1
cmꢃ1): n(CO) 1927(vs), 1851(vs). H NMR (500 MHz,
CDCl3, 298 K): d 1.10 (d, 3J(HH)ꢀ
/
9.2 Hz, 1H, Hanti),
1.64 (m, 1H, Hanti), 1.80 (d, 4J(HH)ꢀ
/
6.3 Hz, 3H,
Complex
endo-,
exo-[Mo{h3-C3H4(CH3)}(h2-
3
CH3), 1.91 (s, 4H, NCH2CH2), 2.94 (d, J(HH)ꢀ
/
6.4
Hz, 1H, Hsyn), 3.52 (s, 4H, NCH2), 3.75 (m, 1H, Hc).
S2CNC4H8)(CO)(h2-dppe)] (3) was synthesized using
the same procedure as that used in the synthesis of 2 by
employing 1 and dppe. The yields are 95% for 3.
13C{1H} NMR (75 MHz, CDCl3, 298 K): d 18.5 (s,

276
K.-H. Yih et al. / Inorganica Chimica Acta 348 (2003) 271ꢁ278
/
Spectroscopic data of endo-, exo-3 are as follows. IR
rection, based on the azimuthal scan data, was applied
to the data. Crystallographic computations were carried
out on a Microvax III computer using the NRCC-SDP-
VAX structure determination package [10].
A suitable single crystal of 2 was mounted on the top
of a glass fiber with glue. Initial lattice parameters were
determined from 24 accurately centered reflections with
u values in the range from 2.08 to 27.508. Cell constants
and other pertinent data were collected and are recorded
in Table 1. Reflection data were collected using the u/2u
scan method. The u scan angle was determined for each
(KBr, cmꢃ1): n(CO) 1790(vs). 1H NMR (500 MHz,
CDCl3, 298 K): d 1.46, 1.59, 1.66 (m, 4H, NCH2CH2),
1.98 (s, 3H, CH3), 2.08 (d, 4J(HH) 6.06 Hz, 2H, Hanti),
2.25 (br, 1H, Hsyn), 2.76, 2.85, 3.25 (m, 4H, NCH2),
2.49, 2.98 (m, 4H, PCH2), 4.06 (m, 1H, Hc). 13C{1H}
NMR (75 MHz, CDCl3, 298 K): d 18.8, 19.7 (s, CH3),
24.6, 24.9 (s, NCH2CH2), 26.2 (t, J(PC)ꢀ
PCH2), 48.7, 49.2 (s, NCH2), 77.2 (s, CH2ÄCH), 88.6 (s,
CH2ÄCH), 125.4ꢁ136.1 (Ph), 203.8, 205.7 (s, CS2). MS
(FAB, NBA, m/z) 697.7 (Mꢂ ꢁ
CO). Anal. Calc. for
/19.8 Hz,
/
/
/
/
C36H39NOP2S2Mo: C, 59.74; H, 5.43; N, 1.94%. Found:
C, 59.66; H, 5.20; N, 1.78%. 31P{1H} NMR (202 MHz,
CDCl3, 298 K): endo-3: d 56.2, 85.0 (br, dppm). exo-3:
reflection according to the equation 0.7090.35 tan u.
/
Three check reflections were measure every 30-min
throughout the data collection and showed no apparent
decay. The merging of equivalent and duplicate reflec-
tions gave a total of 26 013 unique measured data, of
2
d 65.0, 88.3 (d, J(PP)ꢀ
/
29.8 Hz, dppm).
which 7347 reflections with I ꢀ2s(I) were considered.
/
3.5. X-ray crystallography
The first step of the structure solution used the heavy-
atom method (Patterson synthesis), which revealed the
positions of metal atoms. The remaining atoms were
found in a series of alternating difference Fourier maps
and least-squares refinements. The quantity minimized
Single crystal of exo-2 suitable for X-ray diffraction
analysis was grown by recrystallization from 20/1 n-
hexane/CH2Cl2. The diffraction data were collected at
room temperature on an Enrafꢁ
/
Nonius CAD4 diffract-
by the least-squares program was w(jFojꢃ
/
jFcj)2, where
ometer equipped with graphite-monochromated Mo Ka
w is the weight of a given operation. The analytical
forms of the scattering factor tables for the neutral
atoms were used [11]. The non-hydrogen atoms were
˚
(lꢀ0.71073 A) radiation. The raw intensity data were
/
converted to structure factor amplitudes and their esd’s
after corrections for scan speed, background, Lorentz,
and polarization effects. An empirical absorption cor-
Table 2
Selected bond distances (A) and angles (8) for exo-[Mo{h3-
˚
C3H4(CH3)}(h2-S2CNC4H8)(CO)(h2-dppm)] (2)
Table 1
Crystal data and refinement details for complex exo-[Mo{h3-
C3H4(CH3)}(h2-S2CNC4H8)(CO)(h2-dppm)] (2)
Bond distances
MoÃ
MoÃ
MoÃ
MoÃ
MoÃ
MoÃ
MoÃ
MoÃ
C(6)Ã
/
S(1)
S(2)
C(1)
C(2)
C(3)
C(4)
P(1)
P(2)
2.5324(10)
2.6197(10)
1.902(4)
C(2)Ã
C(3)Ã
C(4)Ã
C(1)Ã
P(1)Ã
P(2)Ã
S(1)Ã
S(2)Ã
/
C(3)
C(4)
C(5)
O(1)
1.393(6)
1.393(6)
1.495(6)
1.185(5)
1.841(4)
1.838(4)
1.726(4)
1.704(4)
Empirical formula
Formula weight
Crystal system
Crystal size (mm)
Space group
C35H37NOP2S2Mo
709.66
Trigonal
/
/
/
/
/
2.329(4)
/
0.28ꢄ
/
0.25ꢄ0.15
/
/
2.337(4)
/C(11)
P31
/
2.404(4)
/C(11)
˚
a (A)
11.2966(1)
11.2966(1)
22.6575(2)
120
/
2.4754(10)
2.4298(10)
1.333(5)
/
C(6)
C(6)
˚
b (A)
/
/
˚
c (A)
/N(1)
g (8)
3
V (A )
Bond angles
S(1)ÃMoÃ
S(1)ÃMoÃ
S(1)ÃMoÃ
S(1)ÃMoÃ
S(1)ÃMoÃ
S(2)ÃMoÃ
S(2)ÃMoÃ
S(2)ÃMoÃ
S(2)ÃMoÃ
C(1)ÃMoÃ
C(1)ÃMoÃ
C(1)ÃMoÃ
C(2)ÃMoÃ
C(2)ÃMoÃ
C(3)ÃMoÃ
C(4)ÃMoÃ
C(3)ÃMoÃ
C(4)ÃMoÃ
˚
2504.02(4)
3
/
/
S(2)
C(1)
C(2)
C(3)
C(4)
C(1)
C(2)
C(3)
C(4)
68.68(3)
100.52(12)
135.58(10)
113.30(12)
79.51(10)
169.11(12)
86.4(12)
S(l)Ã
S(1)Ã
S(2)Ã
S(1)Ã
S(1)Ã
S(2)Ã
S(2)Ã
C(1)Ã
C(1)Ã
P(1)ÃMoÃ
P(1)ÃC(11)Ã
C(5)ÃC(4)ÃMo
C(6)ÃN(1)Ã
C(6)ÃN(1)Ã
MoÃS(2)Ã
MoÃS(1)Ã
C(7)Ã
MoÃC(1)Ã
/
C(6)Ã
C(6)Ã
C(6)Ã
MoÃ
MoÃ
MoÃ
MoÃ
MoÃ
MoÃ
/
S(2)
115.9(2)
122.0(3)
122.1(3)
143.93(4)
77.55(3)
89.81(3)
101.74(3)
89.13(11)
87.86(12)
67.48(3)
95.58(18)
70.3(2)
Z
/
/
/
/N(1)
T (K)
DCalc. (g cmꢃ3
150(1)
1.412
0.642
/
/
/
/N(1)
)
m (Mo Ka) (mmꢃ1
F(000)
)
/
/
/
/
P(2)
P(1)
P(1)
P(2)
/
/
/
/
1098
/
/
/
/
u Range
h,k,l range
2.08ꢁ/27.50
/
/
/
/
ꢃ
/
140
/
14, ꢃ
/
140/14, ꢃ
/
29026
/
/
/
101.30(11)
84.82(10)
101.12(16)
81.35(15)
91.93(15)
140.78(11)
75.11(10)
102.60(12)
156.83(10)
166.63(11)
135.68(10)
/
/
P(1)
P(2)
Reflections collected
26 013
7347
398
/
/
/
/
Observed data [I ꢀ2s(I)]
/
/
/
C(2)
C(3)
C(4)
P(1)
P(2)
P(2)
P(1)
P(1)
P(2)
/
/
P(2)
No. of parameters
Ra
/
/
/
/P(2)
0.040
0.090
b
Rw
/
/
/
/
/
/
/
/C(7)
123.9(4)
123.4(4)
86.40(14)
88.79(14)
112.2(4)
178.6(3)
Transmission (min, max)
Quality-of-fitc
˚
0.911, 0.824
1.064
/
/
/
/C(10)
3
/
/
/
/
C(6)
D(D-map) max, min (e A )
ꢃ/0.594; 0.774
/
/
/
/
C(6)
a
/
/
/
N(1)Ã
/C(10)
Rꢀ
/
SjjFojꢃ
Rwꢀ
[Sv(jFojꢃ
Quality-of-fitꢀ
/
jFcjj/SjFoj.
b
c
/
/
/
/
O(1)
/
/
jFcj)2]1/2; vꢀ1/s2(jFoj).
/
[Sv(jFojꢃ
/
jFcj/)2/(Nreflections
ꢃ .
Nparameters)]1/2
/

K.-H. Yih et al. / Inorganica Chimica Acta 348 (2003) 271ꢁ
/278
277
Table 3
Selected bond distances (A) and angles (8) for exo-[Mo{h3-C3H4(CH3)}(h2-S2CNC4H8)(CO)(h2-dppm)] (2) and exo-[Mo(h3-C3H5)(h2-
˚
S2CNC4H8)(CO)(h2-dppm)]
refined anisotropically. Hydrogen atoms were included
in the structure factor calculations in their expected
positions on the basis of idealized bonding geometry but
were not refined in least squares. The final residuals of
structure factors (15 pages) are available from the
author K.H. Yih upon request.
Acknowledgements
this refinement were Rꢀ
/
0.040 and Rwꢀ0.090. Selected
/
bond distances and angles are listed in Table 2.
We thank the National Science Council of the
Republic of China for support.
4. Supplementary material
References
Tables of complete atomic coordinates, bond lengths
and angles, thermal parameters (4 pages) and listing of
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