Allyl complexes of molybdenum with Schiff base ligands. The crystal structures of (η3-C3H5)] are described

Article abstract of DOI:10.1016/S0022-328X(02)01778-3

Treatment of the molybdenum tetracarbonyl complexes of [Mo(CO) ₄L₂](L₌/pyridyl amine Schiff base ligands) with allyl chloride in refluxing THF afforded η³ -allyl complexes [MoCl(CO)₂L₂(η

Full text of DOI:10.1016/S0022-328X(02)01778-3

Journal of Organometallic Chemistry 660 (2002) 91Á97
/
www.elsevier.com/locate/jorganchem
Allyl complexes of molybdenum with Schiff base ligands. The crystal
structures of [MoCl(CO)2{N(C6H4-2-OMe)Ä
C(Me)C5H4N}(h3-
C(Ph)C5H4N}(h3-C3H5)] are
/
C3H5)] and [MoCl(CO)2{N(Me)Ä
/
described
Ayfer Mentes a,*, Raymond D.W. Kemmitt b, John Fawcett c, David R. Russell c
a Department of Chemistry, Arts and Science Faculty, Zonguldak Karaelmas University, 67100 Zonguldak, Turkey
b Department of Chemistry, Inorganic Research Laboratories, The University of Leicester, Leicester LE1 7RH, UK
c Department of Chemistry, X-ray Crystallography Laboratory, The University of Leicester, Leicester LE1 7RH, UK
Received 20 July 2002; received in revised form 20 July 2002; accepted 2 August 2002
Abstract
Treatment of the molybdenum tetracarbonyl complexes of [Mo(CO)4L2] (L2ꢀ
chloride in refluxing THF afforded h3-allyl complexes [MoCl(CO)2L2(h3-allyl)] (1Á
9). These complexes have been characterised by
various techniques including 1H-NMR, IR and FABMS spectroscopies and the single crystal X-ray structure determinations of the
/pyridyl amine Schiff base ligands) with allyl
/
complexes [MoCl(CO)2{N(C6H4-2-OMe)Ä
/
C(Me)C5H4N}(h3-C3H5)] (3) and [MoCl(CO)2{N(Me)ÄC(Ph)C5H4N}(h3-C3H5)] (4).
/
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Allyl; Carbonyl; Molybdenum; Pyridyl amine; Schiff base; X-ray structure
1. Introduction
base) with an excess of the appropriate allyl halide in
refluxing THF (Scheme 1). These complexes have been
characterised by various techniques including 1H-NMR,
IR and FABMS spectroscopies and the single crystal X-
ray structure determinations of the complexes 3 and 4.
The reactions of [Mo(CO)4L2] (L2ꢀ
nitrogen donor ligands) with allyl halides are well
known [1Á11]. We have reported previously the pre-
paration of [M(CO)4L2] (MꢀMo or W; Lꢀpyridyl
amine Schiff base). The cis-[Mo(CO)4L2] complexes are
prepared by treatment of cis-[Mo(CO)4(pip)2] (pipꢀ
/
phosphine and
/
/
/
Analogous reactions of [W(CO)4L2] (L2ꢀ
/
pyridyl amine
Schiff base) with allyl halides were unsuccessful.
/
Treatment of complex [MoCl(CO)2({N(Me)Ä
C(Me)C5H4N})(h3-C3H5)] (1) with one equivalent of
triphenylphosphine in the presence of potassium hexa-
fluorophosphate in refluxing acetonitrile afforded the
/
piperidine) with 2-acetyl or 2-benzoyl pyridine and the
appropriate imine in refluxing i-PrOH [12,13].
cationic complex [Mo(CO)2{N(Me)Ä
/
C(Me)C5H4N}-
(PPh3)(h3-C3H5)][PF6] (10). Complex 10 is less soluble
in common organic solvents and was characterised by
IR, 1H-NMR, 31P-{1H} and FABMS spectroscopy.
Complex 1 also reacted with potassium thiocynate in
2. Results and discussion
Allyl complexes of the type [MoCl(CO)2L2(h3-R-
allyl)], (1Á
/
9), (L2ꢀ
/
pyridyl amine Schiff base, RꢀH,
/
1-Me or 2-Me) can be prepared successfully by the
acetone to form [Mo(NCS)(CO)2{N(Me)Ä
/
C(Me)-
C5H4N}(h3-C3H5)] (11). The brown insoluble solid
was characterised by IR, H-NMR and FABMS spec-
treatment of [Mo(CO)4L2] (L2ꢀpyridyl amine Schiff
/
1
troscopy.
The crystal structures of complexes 3 and 4 have been
determined. The molecular structure of the complexes 3
* Corresponding author. Tel.: ꢁ
2574-181
E-mail address: mentes@karaelmas.edu.tr (A. Mentes).
/
90-272-2577-225; fax: ꢁ90-372-
/
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 7 7 8 - 3

92
A. Mentes et al. / Journal of Organometallic Chemistry 660 (2002) 91Á
/97
Scheme 1.
and 4 are shown in Figs. 1 and 2, which also give the
crystallographic numbering scheme. Selected bond dis-
tances and angles are given in Tables 1 and 2. The
complexes have a distorted octahedral arrangement of
ligands around molybdenum. The central carbon of the
allyl group is trans to the carbonyl ligands. The angles
between the allyl group planes and the Mo(CO)2 planes
are 6.9 and 6.78, respectively for 3 and 4. The pyridyl
amine Schiff base ligand planes lie 16.5 and 17.98 below
the horizontal Mo(CO)2 planes for the complexes 3 and
4, respectively.
˚ ˚
The MoÁ
/
N(1) and MoÁN(2) [2.258(4) A, 2.240(3) A]
/
distances in complex 3 are similar to those of the
literature complexes [Mo(NCS)(CO)2(bipy)(h3-C3H5)]
(12) [2.256(7) A, 2.189(7) A] and [Mo(NCS)(CO)2-
˚
˚
3
˚
˚
(phen)(h -2-Me-C3H4)] (13) [2.252(8) A, 2.255(8) A],
respectively [8,9]. The MoÁN(1) and MoÁN(2) [2.243(3)
A, 2.233(3) A] distances in complex 4 are similar to
those of the literature complex [Mo(CO)4{N(Me)Ä
/
/
˚
˚
/
˚
˚
C(Ph)C5H4N}] [2.228(2) A, 2.241(2) A], respectively
˚
[12]. The central allyl carbon atom [2.203(5) A] and
˚
[2.205(4) A] is closer to the molybdenum atom than the
˚
two terminal carbon atoms [2.318(5) A, 2.313(5) A] and
˚
˚
˚
[2.320(5) A, 2.319(4) A] for the complexes 3 and 4,
respectively. The allylic inter-carbon angle 3 [115.4(5)8]
and 4 [116.5(5)8] compare well with those of the
complexes 12 [115.7(11)8] and 13 [111.5(1)8].
1
The room temperature H-NMR spectra of all com-
1
plexes are consistent with the structure. The H-NMR
spectrum of a typical h3-allyl complex shows three
signals for the allyl group from three sets of protons,
central (Hc), syn (Hs) and anti (Ha). The anti protons
appear as a doublet in the region 1.10Á
6.9Á11.2 Hz), while the doublet due to the syn protons
occur between 2.29 and 3.90 ppm (Jꢀ3.3Á6.6 Hz). The
multiplet assigned to the central allylic proton appears
in the range 2.93Á3.84 ppm. However, complexes 1, 3
and 4 show two sets of signals indicating the presence of
/
1.52 ppm (Jꢀ
/
/
/
/
/
Fig. 1. Molecular structure of 3 showing the atom numbering scheme.
Displacement parameters are shown at the 30% level.

A. Mentes et al. / Journal of Organometallic Chemistry 660 (2002) 91Á
/97
93
Fig. 2. Molecular structure of 4 showing the atom numbering scheme. Displacement parameters are shown at the 30% level.
Table 1
Table 2
˚
˚
Selected bond lengths (A) and bond angles (8) with estimated standard
deviations in parenthesis for 3
Selected bond lengths (A) and bond angles (8) with estimated standard
deviations in parenthesis for 4
Bond lengths
Bond lengths
MoÁ
MoÁ
MoÁ
MoÁ
MoÁ
MoÁ
MoÁ
MoÁ
N(1)Á
/
C(1)
C(2)
C(3)
C(4)
C(5)
N(1)
N(2)
Cl
1.959(5)
1.947(5)
2.318(5)
2.203(5)
2.313(5)
2.258(4)
2.240(3)
2.4835(13)
1.441(6)
N(1)Á
N(2)Á
N(2)Á
C(1)Á
C(2)Á
C(3)Á
C(4)Á
O(3)Á
O(3)Á
/
C(13)
C(15)
C(19)
1.285(5)
1.367(5)
1.326(5)
1.148(6)
1.158(5)
1.408(7)
1.394(6)
1.420(6)
1.372(5)
MoÁ
MoÁ
MoÁ
MoÁ
MoÁ
MoÁ
MoÁ
MoÁ
/
C(1)
C(2)
C(3)
C(4)
C(5)
N(1)
N(2)
Cl
1.962(5)
1.954(3)
2.320(5)
2.205(4)
2.319(4)
2.243(3)
2.233(3)
2.4874(9)
N(1)Á
N(1)Á
N(2)Á
N(2)Á
C(1)Á
C(2)Á
C(3)Á
C(4)Á
/
C(6)
C(7)
C(8)
C(12)
1.462(5)
1.286(4)
1.370(4)
1.337(5)
1.147(5)
1.148(4)
1.385(7)
1.394(7)
/
/
/
/
/
/
/
/
/
/
O(1)
O(2)
C(4)
C(5)
/
/
/
/
/
/
O(1)
O(2)
C(4)
C(5)
/
/
/
/
/
/
/
/
/
/C(6)
/
/
/C(12)
/C(7)
Bond angles
C(2)ÁMoÁ
C(1)ÁMoÁ
C(2)ÁMoÁ
C(1)ÁMoÁ
C(1)ÁMoÁ
C(2)ÁMoÁ
C(2)ÁMoÁ
O(1)ÁC(1)Á
Bond angles
C(2)ÁMoÁ
C(1)ÁMoÁ
C(2)ÁMoÁ
C(1)ÁMoÁ
C(1)ÁMoÁ
C(2)ÁMoÁ
C(2)ÁMoÁ
O(1)ÁC(1)Á
O(2)ÁC(2)Á
/
/
C(1)
C(4)
C(4)
N(1)
N(2)
N(1)
N(2)
81.0(2)
104.3(2)
103.7(2)
99.6(1)
O(2)Á
C(3)Á
C(1)Á
C(2)Á
C(4)Á
N(1)Á
N(2)Á
N(1)Á
/
C(2)Á
/
Mo
C(5)
177.5(5)
116.5(5)
88.4(1)
87.2(1)
164.4(1)
81.5(1)
80.2(1)
72.5(1)
/
/
C(1)
C(4)
C(4)
N(1)
N(2)
N(1)
N(2)
80.0(2)
104.3(2)
104.2(2)
168.2(2)
103.2(2)
103.2(2)
169.1(2)
177.2(5)
178.3(5)
C(3)Á
C(1)Á
C(2)Á
C(4)Á
N(1)Á
N(2)Á
N(1)Á
C(7)Á
O(3)Á
/
C(4)Á
MoÁCl
MoÁ
MoÁ
MoÁ
MoÁ
MoÁ
/
C(5)
115.4(5)
87.4(2)
89.0(1)
/
/
/
C(4)Á
/
/
/
/
/
/
/
/
MoÁ
MoÁ
MoÁ
MoÁ
MoÁ
MoÁ
/
Cl
Cl
Cl
/
/
/
/Cl
/
/
/
/
/
/
/
/Cl
163.6(1)
81.38(10)
80.68(10)
71.73(13)
118.2(4)
124.8(5)
/
/
166.9(1)
168.6(1)
104.8(2)
177.9(4)
/
/
/
/
/
/
Cl
/
/
/
/
Cl
/
/
/
/
Cl
/
/
/
/
Cl
/
/
/
/
N(2)
/
/Mo
/
/
N(2)
/
/Mo
/
O(3)Á
/
C(6)
C(8)
/
/Mo
/
C(7)Á
/
a 2-methyl substituted allyl group, are less complicated
than those for the h3-C3H5 complexes. This is due to the
replacement of the central proton by a methyl group,
therefore removing coupling to the terminal protons.
two isomers in a 3:1 ratio. The two isomers are due to
the allyl group taking up different orientations which
are slow to interconvert on the NMR timescale at room
temperature. Solubility problems inhibited a study of
The methyl groups appear in the range 1.22Á
/
1.43 ppm
with the anti protons 1.31Á1.34 ppm and the syn
/
1
1
the low temperature H-NMR spectra. The H-NMR
spectra of complexes 6 and 7, where the allyl group is the
1-methyl substituted allyl, are much more complex. This
is due to the complexes being unsymmetrical, hence
making all the protons inequivalent in the molecules.
protons appearing between 2.69 and 2.96 ppm.
The nitrogen donor ligands and phenyl group all have
multiplets in the aromatic region of the spectra between
6.68 and 9.38 ppm. The methyl group bonded to
nitrogen appears as a singlet between 3.38 and 4.18
ppm. The methyl group bonded to carbon also appears
1
The H-NMR spectra of complexes 8 and 9, containing

94
A. Mentes et al. / Journal of Organometallic Chemistry 660 (2002) 91Á97
/
as a singlet between 2.23 and 2.54 ppm. The spectrum of
complex 3 also showed a singlet at 3.92 ppm for the
OMe which is bonded to the two-position of the phenyl
group.
The infrared spectra of the complexes [MoCl(CO)2L2-
(h3-allyl)] exhibited two bands of approximately equal
intensity in the carbonyl stretching region between 1945
and 1840 cmꢂ1 as expected for a cis geometry of
carbonyl groups around the metal. The complexes also
Calc.: C, 42.85; H, 4.12; N, 7.69%. IR: 1940, 1840
n(CO), 1598 n(NÄ
C) cmꢂ1. Mass spectrum: [MH]ꢁ at
m/z 364, [MHꢂ
Cl]ꢁ 329, [MHꢂ2CO]ꢁ 308. 1H-
NMR: isomer a: 8.78Á7.26 (4H, m, Arom.), 4.18 (3H,
s, NÁCH3), 2.54 (3H, s, CÁCH3), 1.30 (2H, d, Jꢀ11.2
Hz, anti-CH), 3.20 (2H, br, syn-CH), 3.84 (1H, m,
central CH). isomer b: 8.78Á7.26 (4H, m, Arom.), 3.68
(3H, s, NÁCH3), 2.39 (3H, s, CÁCH3), 1.48 (2H, d, Jꢀ
/
/
/
/
/
/
/
/
/
/
/
8.2 Hz, anti-CH), 2.98 (2H, br, syn-CH), 3.77 (1H, m,
central CH).
showed n(CÄ
/
N) stretching frequencies in the region of
.
1580Á
/
1600 cmꢂ1
The FABMS spectra show parent ions and fragmen-
tation due to loss of the chloride and successive carbonyl
ligands.
3.2. Preparation of [MoCl(CO)2{N(Ph)Ä
/
C(Me)C5H4N}((h3-C3H5)] (2)
Using the same procedure as for 1 a mixture of
[Mo(CO)4{N(Ph)Ä
/
C(Me)C5H4N}] (0.3 g, 0.74 mmol)
3. Experimental
and excess allyl chloride (0.940 g, 0.012 mol) was
refluxed in THF (10 cm3) for 3 h to afford the title
complex as a dark purple solid 2. Yield 0.120 g (38%
based on Mo). Anal. Found: C, 50.83; H, 3.81; N, 6.74.
C18H17ClMoN2O2 Calc.: C, 50.59; H, 3.98; N, 6.54%.
All reactions were performed under a dry, oxygen-
free, nitrogen atmosphere, using solvents which were
dried and distilled under nitrogen just prior to use. Light
petroleum ether refers to the fraction that boils in the
IR: 1930, 1850, n(CO), 1600 n(NÄ
spectrum: [MH]ꢁ at m/z 426, [MHꢂCl]ꢁ 389, [MHꢂ
7.07 (9H, m, Arom.), 2.23
CH3), 1.38 (1H, d, Jꢀ9.1 Hz, anti-CH), 1.08
(1H, d, Jꢀ9.3 Hz, anti-CH), 3.10 (2H, br, syn-CH),
3.54 (1H, m, central CH).
/
C) cmꢂ1. Mass
40Á
/
608 range. Microanalysis were carried out by either
/
/
1
Butterworth Laboratories Ltd., UK or TUBITAK-
Marmara Research Centre, Turkey. The FAB mass
spectrum of the solid complexes were obtained on a
Kratos Concept double focusing sector mass spectro-
meter. The 1H-NMR spectra were recorded at room
temperature (r.t.) in [2H1]chloroform on a Bruker
AM300 spectrometer operating at 300.13 MHz with
2CO]ꢁ 370. H-NMR: 9.22Á
/
(3H, s, CÁ
/
/
/
3.3. Preparation of [MoCl(CO)2{N(C6H4-2-OMe)Ä
/
C(Me)C5H4N}(h3-C3H5)] (3)
SiMe4 (0.0 ppm) as internal reference. The 31PÁ{1H}-
/
NMR were recorded at r.t. in dicholoromethane on a
JEOL JNM-FX90 spectrometer operating at 36.2 MHz
with [P(OH)4]ꢁ in [2H2]-water (0.0 ppm) as external
reference. The quoted IR spectra were recorded on a
Using the same procedure as for 1 a mixture of
[Mo(CO)4{N(C6H4-2-OMe)Ä/C(Me)C5H4N}] (0.4 g,
0.92 mmol) and excess allyl chloride (0.940 g, 0.012
mol) was refluxed in THF (10 cm3) for 3 h to afford the
title complex as a dark purple solid 3. Yield 0.260 g (62%
based on Mo). Anal. Found: C, 49.88; H, 4.24; N, 6.02.
C19H19ClMoN2O3 Calc.: C, 50.11; H, 4.18; N, 6.15%.
PerkinÁ
/
Elmer 580B spectrophotometer in Nujol mulls
600 cmꢂ1
between NaCl plates in the range 3000Á
/
.
Allyl chloride, 3-chloro-2-methyl-1-propene and 1-
chloro-3-methyl-1-propene were used as supplied from
IR: 1940, 1840, n(CO), 1590 n(NÄ
spectrum: [MH]ꢁ at m/z 456, [MHꢂCl]ꢁ 421, [MHꢂ
2CO]ꢁ 400. 1H-NMR: isomer a: 9.37Á
6.68 (8H, m,
Arom.), 3.92 (3H, s, OÁCH3), 2.24 (3H, s, CÁCH3),
1.40 (2H, d, Jꢀ9.7 Hz, anti-CH), 3.13 (2H, br, syn-
CH), 3.66 (1H, m, central CH). Isomer b: 9.37Á6.68
(8H, m, Arom.), 3.88 (3H, s, OÁCH3), 2.16 (3H, s, CÁ
CH3), 1.10 (2H, d, Jꢀ9.5 Hz, anti-CH), 2.29 (2H, br,
syn-CH), 2.93 (1H, m, central CH).
/
C) cmꢂ1. Mass
Aldrich. The complexes [Mo(CO)4L2] (L2ꢀ
/
pyridyl
/
/
amine Schiff base ligands), were prepared as described
in the literature [12,13].
/
/
/
/
3.1. Preparation of [MoCl(CO)2{N(Me)Ä
/
/
C(Me)C5H4N}(h3-C3H5)] (1)
/
/
/
A
mixture of [Mo(CO)4{N(Me)Ä/C(Me)C5H4N}]
(0.648 g, 2 mmol) and excess allyl chloride (0.940 g,
0.012 mol) was refluxed in THF (10 cm3) for 3 h. The
resulting dark purple solution was cooled to r.t. and the
addition of light petroleum ether precipitated a dark
purple solid which was filtered, washed with light
petroleum ether and dried in vacuo. Recrystallisation
from dichloromethane/diethyl ether yielded the title
complex 1. Yield 0.42 g (58% based on Mo). Anal.
Found: C, 42.41; H, 4.29; N, 7.16. C13H15ClMoN2O2
3.4. Preparation of [MoCl(CO)2{N(Me)Ä
/
C(Ph)C5H4N}(h3-C3H5)] (4)
Using the same procedure as for 1 a mixture of
C(Ph)C5H4N}] (0.2 g, 0.5 mmol)
[Mo(CO)4{N(Me)Ä
/
and excess allyl chloride (0.940 g, 0.012 mol) was
refluxed in THF (10 cm3) for 3 h to afford the title
complex as a dark purple solid 4. Yield 0.1 g (50% based

A. Mentes et al. / Journal of Organometallic Chemistry 660 (2002) 91Á
/97
95
on Mo). Anal. Found: C, 49.88; H, 3.90; N, 6.45.
C18H17ClMoN2O2 Calc.: C, 50.58; H, 3.98; N, 6.56%.
spectrum: [MH]ꢁ at m/z 441, [MHꢂ
/
Cl]ꢁ 405, [MHꢂ
7.16 (9H, m, Arom.), 3.38
CH3), 1.55 (m), 1.67 (m), 2.35 (m), 2.97 (s),
/
1
2CO]ꢁ 384. H-NMR: 8.94Á
(3H, s, NÁ
3.60(m).
/
IR: 1935, 1850, n(CO), 1580 n(NÄ
spectrum: [MH]ꢁ at m/z 426, [MHꢂCl]ꢁ 391, [MHꢂ
2CO]ꢁ 370. 1H-NMR: isomer a: 9.15Á
7.11 (9H, m,
Arom.), 3.96 (3H, s, NÁCH3), 1.36 (2H, d, Jꢀ6.9 Hz,
anti-CH), 3.90 (2H, d, Jꢀ3.3 Hz, syn-CH), 3.20 (1H,
m, central CH). Isomer b: 9.15Á7.11 (9H, m, Arom.),
3.45 (3H, s, NÁCH3), 1.52 (2H, d, Jꢀ8.8 Hz, anti-CH),
3.30 (2H, d, Jꢀ3.4 Hz, syn-CH), 3.10 (1H, m, central
CH).
/
C) cmꢂ1. Mass
/
/
/
/
/
/
3.8. Preparation of [MoCl(CO)2{N(Me)Ä
/
/
C(Me)C5H4N}(h3-2-MeC3H4)] (8)
/
/
/
Using the same procedure as for 1 a mixture of
/
[Mo(CO)4{N(Me)Ä
/
C(Me)C5H4N}] (0.205 g, 0.6 mmol)
and excess 3-chloro-2-methyl-propene (0.920 g, 0.010
mol) was refluxed in THF (10 cm3) for 3 h to afford the
title complex as a dark purple solid 8. Yield 0.150 g (66%
based on Mo). Anal. Found: C, 44.12; H, 4.42; N, 7.23.
C14H17ClMoN2O2 Calc.: C, 44.39; H, 4.49; N, 7.39%.
3.5. Preparation of [MoCl(CO)2{N(Ph)Ä
/
C(Ph)C5H4N}(h3-C3H5)] (5)
Using the same procedure as for 1 a mixture of
C(Ph)C5H4N}] (0.3 g, 0.64 mmol)
IR: 1928, 1850, n(CO), 1590 n(NÄ
spectrum: [MH]ꢁ at m/z 378, [MHꢂCl]ꢁ 343, [MHꢂ
7.25 (4H, m, Arom.), 3.68
CH3), 2.43 (3H, s, CÁCH3), 1.22 (3H, s,
/
C) cmꢂ1. Mass
[Mo(CO)4{N(Ph)Ä
/
/
/
1
and excess allyl chloride (0.940 g, 0.012 mol) was
refluxed in THF (10 cm3) for 3 h to afford the title
complex as a dark purple solid 5. Yield 0.06 g (20%
based on Mo). Anal. Found: C, 56.55; H, 4.05; N, 5.33.
C23H19ClMoN2O2 Calc.: C, 56.67; H, 3.90; N, 5.75%.
2CO]ꢁ 322. H-NMR: 8.77Á
/
(3H, s, NÁ
/
/
CH3), 1.31 (1H, s, anti-CH), 1.34 (1H, s, anti-CH), 2.69
(1H, s, syn-CH), 2.86 (1H, s, syn-CH).
IR: 1945, 1850, n(CO), 1585 n(NÄ
spectrum: [MH]ꢁ at m/z 488 [MHꢂCl]ꢁ 453, [MHꢂ
2CO]ꢁ 432. 1H-NMR: 9.28Á
7.04 (14H, m, Arom.), 1.45
(2H, d, Jꢀ9.3 Hz, anti-CH), 3.65 (2H, d, Jꢀ6.6 Hz,
syn-CH), 3.13 (1H, m, central CH).
/
C) cmꢂ1. Mass
3.9. Preparation of [MoCl(CO)2{N(Me)Ä
/
/
/
C(Ph)C5H4N}(h3-2-MeC3H4)] (9)
/
/
/
Using the same procedure as for 1 a mixture of
[Mo(CO)4{N(Me)Ä
/
C(Ph)C5H4N}] (0.2 g, 0.5 mmol)
and excess 3-chloro-2-methyl-propene (0.920 g, 0.010
mol) was refluxed in THF (10 cm3) for 3 h to afford the
title complex as a dark purple solid 9. Yield 0.180 g (82%
based on Mo). Anal. Found: C, 51.23; H, 4.45; N, 6.30.
C19H19ClMoN2O2 Calc.: C, 51.70; H, 4.31; N, 6.35%.
3.6. Preparation of [MoCl(CO)2{N(Me)Ä
/
C(Me)C5H4N}(h3-1-MeC3H4)] (6)
Using the same procedure as for 1 a mixture of
[Mo(CO)4{N(Me)ÄC(Me)C5H4N}] (0.4 g, 1.16 mmol)
/
IR: 1930, 1855, n(CO), 1590 n(NÄ
spectrum: [M]ꢁ at m/z 440, [MꢂCl]ꢁ 405, [Mꢂ
2CO]ꢁ 384. 1H-NMR: 8.80Á
7.15 (9H, m, Arom.),
3.44 (3H, s, NÁCH3), 1.32 (2H, s, anti-CH), 1.43 (3H,
s, CH3), 2.81 (1H, s, syn-CH), 2.96 (1H, s, syn-CH).
/
C) cmꢂ1. Mass
and excess crotyl chloride (0.930 g, 0.010 mol) was
refluxed in THF (10 cm3) for 3 h to afford the title
complex as a dark purple solid 6. Yield 0.07 g (16%
based on Mo). Anal. Found: C, 44.16; H, 4.15; N, 5.88.
C14H17ClMoN2O2 Calc.: C, 44.33; H, 3.85; N, 6.35%.
/
/
/
/
IR: 1925, 1840, n(CO), 1590 n(NÄ
spectrum: [MH]ꢁ at m/z 378, [MHꢂCl]ꢁ 343, [MHꢂ
7.64 (4H, m, Arom.), 3.36
CH3), 2.35 (3H, s, CÁCH3), 1.55 (d, Jꢀ4.7
Hz, CH3), 1.65 (d, Jꢀ5 Hz, CH3), 2.34 (s), 2.98 (s), 4.14
(m, central CH).
/
C) cmꢂ1. Mass
3.10. Preparation of [Mo(CO)2{N(Me)Ä
/
/
/
C(Me)C5H4N}(PPh3)(h3-C3H5)]PF6 (10)
1
2CO]ꢁ 322. H-NMR: 8.73Á
/
(3H, s, NÁ
/
/
/
A mixture of [MoCl(CO)2{N(Me)Ä/C(Me)C5H4N}-
/
(h3-C3H5)] (1) (0.217 g, 0.6 mmol) and triphenylpho-
sphine (0.152 g, 0.6 mmol) and KPF6 (0.110 g, 0.6
mmol) was refluxed in acetonitrile (20 cm3) for 3 h.
After cooling to r.t. the reaction mixture was rotary
evaporated to dryness to yield a red oil. This oil was
dissolved in dichloromethane, filtered to remove potas-
sium chloride and a red solid 10 was precipitated by
addition of diethyl ether. Yield 0.3 g (60%). Anal.
Found: C, 50.80; H, 4.23; N, 3.61. C31H30F6MoN2O2P2
Calc.: C, 50.68; H, 4.09; N, 3.81%. IR: 1940, 1855
3.7. Preparation of [MoCl(CO)2{N(Me)Ä
/
C(Ph)C5H4N}(h3-1-MeC3H4)] (7)
Using the same procedure as for 1 a mixture of
[Mo(CO)4{N(Me)Ä/C(Ph)C5H4N}] (0.3 g, 0.74 mmol)
and excess crotyl chloride (0.930 g, 0.010 mol) was
refluxed in THF (10 cm3) for 3 h to afford the title
complex as a dark purple solid 7. Yield 0.150 g (46%
based on Mo). Anal. Found: C, 51.69; H, 4.26; N, 6.25.
C19H19ClMoN2O2 Calc.: C, 51.70; H, 4.31; N, 6.35%.
n(CO), 1730 n(NÄ
20.79, 157.7 ppm. Mass spectrum: [Mꢂ
591. 1H-NMR ((CD3)2CO): 8.87Á
6.72 (19H, m, Arom.),
3.27 (3H, s, NÁCH3), 2.69 (3H, s, CÁCH3), 2.15 (2H, d,
/
C) cmꢂ1
.
31PÁ
/
{1H}-NMR (CH2Cl2):
PF6]ꢁ at m/z
/
/
IR: 1930, 1845, n(CO), 1600 n(NÄ
/
C) cmꢂ1. Mass
/
/

96
A. Mentes et al. / Journal of Organometallic Chemistry 660 (2002) 91Á97
/
anti-CH), 2.58 (2H, br, syn-CH), 3.50 (1H, m, central
CH).
The geometry of the molecule is shown in Fig. 1.
Selected bond distances and bond angles are listed in
Table 1.
3.11. Preparation of [Mo(NCS)(CO)2{N(Me)Ä
/
C(Me)C5H4N}(h3-C3H5)] (11)
4.2. C18H17ClMoN2O2 (4)
Mꢀ
/
424.73, orthorhombic, space group P212121, aꢀ
/
A mixture of [MoCl(CO)2{N(Me)Ä
/
C(Me)C5H4N}-
˚
(h3-C3H5)] (1) (0.150 g, 0.412 mmol) and potassium
thiocynate (0.04 g, 0.412 mmol) was refluxed in acetone
(10 cm3) for 2 h. After cooling to r.t. the reaction
mixture was rotary evaporated to dryness to yield a
brown oil. This oil was dissolved in dichloromethane,
filtered to remove potassium chloride and a brown solid
was precipitated by addition of diethyl ether. Yield
0.030 g (19%). Anal. Found: C, 44.03; H, 3.84; N, 11.16.
C14H15MoN3O2S Calc.: C, 43.64; H, 3.90; N, 10.91%.
8.066(1), bꢀ
/
12.696(1), cꢀ
4, mꢀ
0.866 mmꢂ1, l(MoÁ
F(000)ꢀ856, Dcalc
1.527 Mg mꢂ3
Conditions were as for 3 except for the following:
crystal size 0.52ꢃ0.42ꢃ
0.40 mm3; intensity data were
collected in the range 2.77Bu B26.498 for 2866 reflec-
/
18.036(1) A, Uꢀ
/
1847.0(3)
3
˚
˚
A , Zꢀ
/
/
/
Ka)ꢀ0.71073 A,
/
/
ꢀ
/
.
/
/
/
/
tion. Absorption correction max. and min. transmission
factors were 0.88 and 0.83, respectively. Final cycles
of refinement gave R1ꢀ
data, R1ꢀ jFcjj/SjFoj, wR2ꢀ
SjjFojꢂ
S w(F2o)2]1/2 1/[s2(F2o)ꢁ(0.024P)2ꢁ
wꢀ
Pꢀ
[max(F2o, 0)ꢁ2F2c]/3. The maximum and minimum
/
0.0241, wR2ꢀ
[S w(F2oꢂ
0.41P] and
/
0.0620 for all
/
/
/
/
F2c)2/
IR: 2083 n(NÅ
cmꢂ1. Mass spectrum [MH]ꢁ at m/z 387. 1H-NMR
((CD3)2SO): 8.75Á7.50 (4H, m, Arom.), 3.58 (3H, s, NÁ
CH3), 2.30 (3H, s, CÁCH3), 1.25 (2H, d, anti-CH), 3.32
/
C), 1935, 1855 n(CO), 1597 n(NÄ
/
C),
,
/
/
/
/
/
/
/
electron densities in the final DF map were 0.24 and
/
˚
ꢂ
/
0.26 e Aꢂ3, respectively.
(2H, br, syn-CH), 3.97 (1H, m, central CH).
The geometry of the molecule is shown in Fig. 2.
Selected bond lengths and angles are given in Table 2.
4. Crystal data
5. Supplementary material
4.1. C19H19ClMoN2O3 (3)
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC nos. 181457 and 181458 for
compounds 3 and 4, respectively. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
Mꢀ
9.971(1), bꢀ
Uꢀ1925.0(4) A , Zꢀ
Ka)ꢀ
/
454.75, monoclinic, space group P21/n, aꢀ
/
˚
/
11.906(2), cꢀ
/
16.249(2) A, bꢀ
/
93.70 (1)8,
3
˚
/
/
4, mꢀ
/
0.841 mmꢂ1, l(MoÁ
/
ꢀ .
1.569 Mg mꢂ3
/
˚
/
0.71073 A, F(000)ꢀ
/
920, Dcalc
A purple crystal was used for data collection with
0.04 mm3 and
approximate dimensions 0.35ꢃ0.23ꢃ
/
/
UK (Fax: ꢁ44-1223-336033; e-mail: deposit@ccdc.
/
was glued to the end of a thin glass fibre using epoxy
resin. Intensity data were measured on a Siemens P4
cam.ac.uk or http://www.ccdc.cam.ac.uk).
diffractometer at 290(2) K, using MoÁ
/
Ka radiation
0.71073 A), and a v-scan method. A total of 4425
reflections were measured over the range 2.51Bu B
25.008 with ꢂ15h 519, ꢂ15k 513 and ꢂ195l 5
19. A semi empirical absorption correction was applied
to the data based on psi scans (max., min. transmission
factors 0.89 and 0.75). The reflections were corrected for
Lorentz and polarisation effects and merged to give
˚
(lꢀ
/
Acknowledgements
/
/
/
/
/
/
/
/
/
/
/
We thank Zonguldak Karaelmas University, Turkey,
for financial support, Johnson Matthey plc for the loan
of palladium metal salts.
3382 independent reflections (Rint
The structures were solved by direct methods and
ꢀ
/
0.0315).
References
refined with full-matrix least-squares on F2 using the
program SHELXTL-PC [14]. The ratio of data:parameters
[1] C.G. Hull, M.H.B. Stiddard, J. Organomet. Chem. 9 (1967) 519.
[2] B.J. Brisdon, D.A. Edwards, J.W. White, J. Organomet. Chem.
156 (1978) 427.
was 3382:235. All non-hydrogen atoms were refined
with anisotropic displacement parameters. Final cycles
[3] H.T. Dieck, H. Friedel, J. Organomet. Chem. 14 (1968) 375.
[4] B.J. Brisdon, K.E. Paddick, J. Organomet. Chem. 149 (1978) 113.
[5] B.J. Brisdon, G.F. Griffin, J. Chem. Soc. Dalton Trans. (1975)
1999.
of refinement gave R1ꢀ
data, R1ꢀ jFcjj/SjFoj, wR2ꢀ
SjjFojꢂ
S w(F2o)2]1/2 1/[s2(F2o)ꢁ(0.0322P)2ꢁ
wꢀ
Pꢀ
[max(F2o, 0)ꢁ2F2c]/3. The maximum and minimum
electron densities in the final DF map were 0.37 and
/
0.0413, wR2ꢀ
[S w(F2oꢂ
0.00P] and
/
0.0830 for all
/
/
/
/
F2c)2/
[6] B.J. Brisdon, M. Cartwright, D.A. Edwards, K.E. Paddick, Inorg.
Chim. Acta 40 (1980) 191.
,
/
/
/
/
/
[7] J.W. Faller, D.A. Haitko, R.D. Adams, D.F. Chodosh, J. Am.
Chem. Soc. 101 (1979) 865.
[8] A.J. Graham, R.H. Fenn, J. Organomet. Chem. 17 (1969) 405.
0.38 e Aꢂ3, respectively.
˚
ꢂ
/

A. Mentes et al. / Journal of Organometallic Chemistry 660 (2002) 91Á
/97
97
[9] A.J. Graham, R.H. Fenn, J. Organomet. Chem. 25 (1970) 173.
˚
[10] L. Eriksson, M.P.T. Sjogren, B. .Akermark, Acta Crystallogr.
¨
[12] A. Mentes, J. Fawcett, R.D.W. Kemmitt, D.R. Russell, Acta
Crystallogr. Sect. C 55 (1999) 48.
[13] A. Mentes, Transition Met. Chem. 24 (1999) 77.
Sect. C 52 (1996) 77.
[11] A.J. Graham, D. Akrigg, B. Sheldrich, Cryst. Struct. Commun. 6
(1977) 253.
[14] G.M. Sheldrick, SHELXTL-PC, Release 6.1, Bruker AXS Analy-
tical X-Ray Instruments, Madison, WI, 1991.