Iron(II)- and cobalt(II) complexes with tridentate bis(imino)pyridine nitrogen ligands bearing chiral bulky aliphatic and aromatic substituents: Crystal structure of [CoCl2{2,6-bis[R-(+)-(bornylimino)methyl] pyridine}]

Article abstract of DOI:10.1002/zaac.200400466

Iron(II) and cobalt(II) complexes (7-15) based on new aldimine 2,6-bis[(imino)methyl]pyridine (1,2,4,6) and ketimine (2,6-bis[(imino)ethyl] pyridine (3,5) ligands with bulky chiral aliphatic or aromatic terminal groups have been prepared and characterized by ¹H NMR, ¹³C NMR, IR-, mass spectroscopy (EI), and elemental analysis. The complex [CoCl ₂(BBoMP)]·1/2 CHCl₃ (13) (BBoMP: 2,6-bis{(R-(+)-(bornylimino)-methyl}pyridine) crystallizes in monoclinic space group P2₁ with cell dimensions: a = 7.6603(11) A, b = 28.3153(14) A, c = 13.537(2) A, V = 2908.1(6) A³, Z = 4. The coordination sphere around Co is distorted trigonal bipyramidal.

Full text of DOI:10.1002/zaac.200400466

Iron(II)- and Cobalt(II) Complexes with Tridentate Bis(imino)pyridine
Nitrogen Ligands Bearing Chiral Bulky Aliphatic and Aromatic Substituents:
Crystal Structure of [CoCl2{2,6-bis[R-(؉)-(bornylimino)methyl]pyridine}]
Kristian Lappalainena, Katariina Yliheikkiläa, Adnan S. Abu-Surrah*,b, Mika Polamoa,
Markku Leskeläa, and Timo Repo*,a
a Helsinki/Finland, Laboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki
b Zarqa/Jordan, Department of Chemistry, Hashemite University
Received October 12th, 2004.
Abstract. Iron(II) and cobalt(II) complexes (7-15) based on new
aldimine 2,6-bis[(imino)methyl]pyridine (1,2,4,6) and ketimine (2,6-
bis[(imino)ethyl]pyridine (3,5) ligands with bulky chiral aliphatic or
aromatic terminal groups have been prepared and characterized by
1H NMR, 13C NMR, IR-, mass spectroscopy (EI), and elemental
analysis. The complex [CoCl2(BBoMP)]·1/2 CHCl3 (13) (BBoMP:
2,6-bis{(R-(ϩ)-(bornylimino)-methyl}pyridine) crystallizes in mo-
˚
noclinic space group P21 with cell dimensions: a ϭ 7.6603(11) A,
3
˚
˚
˚
b ϭ 28.3153(14) A, c ϭ 13.537(2) A, V ϭ 2908.1(6) A , Z ϭ 4. The
coordination sphere around Co is distorted trigonal bipyramidal.
Keywords: Iron; Cobalt; Imines, Tridentate nitrogen ligands
1 Introduction
the aromatic groups in the tridentate ligands influenced not
only the catalytic activity but also the molecular weight and
the microstructure of the resulted polymer material. There-
fore, there is still a great interest to discover and develop
new families of polymerization catalysts that can allow
further control of the polymer microstructure, material
properties and, if possible, capable to polymerize polar vi-
nylic monomers. The late transition metals are less ox-
ophilic than the early transition metals, and are therefore
supposed to be more tolerant toward Lewis bases.
Until the middle of 90’s few reports were introduced about
utilizing late transition metal based complexes as catalyst
precursors for polymerization of α-olefins and ethylene [1].
This is probably because these catalysts generally exhibit
reduced activities for olefin polyinsertion [2]. However, in
1995 new nickel(II) and palladium(II) based catalysts bear-
ing bulky diimine ligands were reported for ethylene poly-
merization [3]. A few years later, late transition metal based
catalysts have attracted increasing attention in the field
homo- and copolymerization of α-olefin [4, 5], especially
after Brookhart’s and Gibson’s reports on new FeII-based
complexes containing 2,6-bis(imino)pyridyl ligands as ef-
ficient catalyst precursors for ethylene polymerization.
After MAO activation these complexes are highly active
and produce strictly linear polyethylene (PE) [6, 7].
As an extension to our studies on both the coordination
chemistry of heteroatom-containing ligands and the cata-
lytic application of their metal complexes [9Ϫ12] we report
here the synthesis and characterization of new 2,6-bis(imi-
no)pyridyl ligands bearing myrtanyl-, bornyl, benzyl or
naphthyl terminals and their corresponding iron(II) and co-
balt(II) complexes. The new compounds were characterized
Recently we reported on highly active 2,6-bis(arylimino)-
pyridine iron(II)- and cobalt(II)-based ethylene polymeriz-
ation catalysts which lack the ortho alkyl substituents on
the aryl groups [8]. Modifications of the steric bulkiness of
1
by elemental analysis, IR-, MS-, H-, and 13C-NMR spec-
troscopy. Furthermore, the complex [CoCl2{2,6-bis[R-(ϩ)-
(bornylimino)methyl]pyridine}] was a subject to X-ray
structural analysis.
* Prof. Adnan S. Abu-Surrah
Department of Chemistry
Hashemite University
2 Results and Discussion
2.1 Ligands and complexes
P.O. Box 150459
Zarqa/Jordan
Tel. ϩ 962 5 382 6600/ ext. 4315
Fax: ϩ 962 5 382 6613
e-mail address: asurrah@hu.edu.jo (Adnan S. Abu-Surrah)
Dr. Timo Repo
Department of Chemistry
University of Helsinki
P. O. B ox 55
Ligand synthesis was based on a classical condensation re-
action where a primary amine is allowed to react with 2,6-
pyridinedicarboxaldehyde or 2,6-diacetylpyridine to form
the corresponding aldimines (2,6-bis[(imino)methyl]pyrid-
ines) (1, 2, 4, and 6) or ketimines (2,6-bis[(imino)ethyl]pyri-
dine) (3, and 5), respectively (Scheme 1). In the case of keti-
mines the reaction requires a catalytic amount of formic
acid while the aldimines form without the acid. The prod-
ucts precipitated nicely from the reaction solution as yellow
or white powder. The reaction can easily be followed by IR
FIN-00014-Finland
Tel. ϩ358 9 191 50230
Fax: ϩ358 9 191 50198
e-mail address: timo.repo@helsinki.fi
Z. Anorg. Allg. Chem. 2005, 631, 763Ϫ768
DOI: 10.1002/zaac.200400466
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
763

K. Lappalainen, K. Yliheikkilä, A. S. Abu-Surrah, M. Polamo, M. Leskelä, T. Repo
Scheme 1
spectroscopy as the strong aldehyde and ketone absorption
bands disappear and new bands appear between 1620 to
1642 cmϪ1 which are due to the stretching vibration of the
imine CϭN bond. The 13C-NMR spectra of the 2,6-bis(imi-
no)pyridine ligands exhibit a singlet signal at about 160-
169 ppm which can be assigned to the imine (CϭN) carbon.
The ketimine ligands showed also a singlet at 13.9
Ϫ17.5 ppm which can be ascribed to the methyl groups in
the backbone of the ligand. The iron(II) aldimine with
penta-coordinated metal atoms (7, 8, 10, and 12) and keti-
mine (9 and 11), as well as cobalt(II), aldimine (13, 14, and
15) complexes were synthesized by treatment of FeCl2 or
CoCl2 with the corresponding 2,6- bis(imino)pyridine li-
gand in THF (Scheme 1). Also the complex synthesis can
be followed by IR spectroscopy as the imine bands shift to
the region of 1530 Ϫ1593 cmϪ1 because of the coordination
[13]. To further confirm the identity of the complexes, a
variety of complimentary techniques including elemental
analysis and mass spectroscopy (EI) were applied.
distortion from the linear arrangement in both molecules.
But, on the other hand, the trigonal plane is fairly regular
having all angles close to 120°( 3) (Table 1). Similar
coordination arrangement was found in a dichloro FeII
complex bearing bis[(2,4,6-trimethylphenyl-imino)ethyl]py-
ridine (BMeEP) [14]. In the same study a dichloro co-
balt(II) complex BPEP-Co(II) (BPEP ϭ 2,6-bis[(2,6-diiso-
propylphenylimino)ethyl]pyridine) bearing similar ligand
with bulkier arylimino substituents, however, crystallized in
a square pyramidal coordination around the metal atom.
The solid state structure of 13 shows that the N-bornyl sub-
stituents do not displace the CoCl2 from the N3Co plane to
the square pyramidal arrangement as was seen in the case
of BPEP-Co(II). Instead, the cobalt atom deviates from the
˚
˚
N3-plane much less (0.0706(3) A and 0.0278(3) A in mol-
˚
ecules A and B, respectively) than in BPEP-Co(II) (0.56 A).
The trigonal bipyramid configuration in 13 fits well to
the C2-symmetry, when the pyridine nitrogen and the cobalt
atom are chosen for a rotation axis. The Co1-N1 (pyridine)
˚
˚
distances (2.031(2) A and 2.027(2) A in mol A and B,
respectively) are only slightly shorter than reported for
2.2 Crystal structure of [CoCl2(BBoMP)]·1/2CHCl3
(13)
˚
BPEP-Co(II), (2.051(3) A), while the Co-N (imino) dis-
tances (molecule A. 2.309(3), 2.350(2) and molecule B
2.260(3) and 2.436(3) are significantly longer than those in
BPEP-Co(II) (2.211(3) and 2.211(3) A). We assume that
The compound 13 crystallizes with two discrete cobalt(II)
complex units and one solvent molecule in the asymmetric
unit. Both complex units are highly similar. The coordi-
nation sphere around the cobalt atom can be roughly classi-
fied as a distorted trigonal bipyramid, in which the imino
nitrogen atoms of the ligand occupy the axial positions and
the two chloride ligands and the nitrogen atom at the pyri-
dine form the trigonal plane (Figure 1). Axial angles (N8a-
Co1a-N8a and N8b-Co1b-N8b (149.93(9))°) show a clear
˚
this difference is due to the change of the imino substituents
from aromatic to aliphatic ones. In addition, the ligand
framework is twisted as shown in the side view picture in
Figure 1.b. The imino nitrogen atoms are shifted opposite
sides of the mean plane, which is established by the pyridine
and the cobalt atom. The chloride ions locate on both sides
of the ligand plane and the Cl-Co-Cl angles (121.21(3)° and
764
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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Z. Anorg. Allg. Chem. 2005, 631, 763Ϫ768

Iron(II)- and Cobalt(II) Complexes with Tridentate Bis(imino)pyridine
Figure 1a
Figure 1b
118.47(4)°) are wider than observed for BPEP-Co(II)
(116.5(1)°) (Table 1).
3 Experimental
3.1 General
˚
Table 1 Selected bond lengths/A and angles/°.
All reactions were carried out under dry argon using standard
Schlenk techniques. All chemicals were commercial and used as
such. Hydrocarbon solvents were purified by refluxing over LiAlH4
or sodium followed by distillation under argon. Methanol was
treated with sodium methoxide/ dimethylterphthalate and sub-
sequently distilled. Solvents were stored under argon atmosphere.
Co1A-N1A
2.031(2)
2.2493(9)
2.2696(9)
2.309(3)
2.350(2)
2.027(2)
2.2426(9)
2.2521(9)
2.260(3)
2.436(3)
117.34(7)
121.11(7)
121.21(3)
75.47(10)
104.91(7)
Cl2A-Co1A-8A
95.06(7)
74.56(10)
91.05(7)
98.18(6)
149.93(9)
121.90(7)
119.38(7)
118.47(4)
76.74(10)
102.93(7)
95.32(7)
73.20(9)
92.18(6)
100.12(6)
149.93(9)
Co1A-Cl1A
Co1A-Cl2A
N1A-Co1A-N20A
Cl1A-Co1A-N20A
Cl2A-Co1A-N20A
N8A-Co1A-N20A
N1B-Co1B-Cl2B
N1B-Co1B-Cl1B
Cl2B-Co1B-Cl1B
N1B-Co1B-N20B
Cl2B-Co1B-N20B
Cl1B-Co1B-N20B
N1B-Co1B-N8B
Cl2B-Co1B-N8B
Cl1B-Co1B-N8B
N20B-Co1B-N8B
Co1A-N8A
Co1A-N20A
Co1B-N1B
Co1B-Cl2B
Co1B-Cl1B
Elemental analyses were performed at the Faculty of Pharmacy,
University of Helsinki (EA 1110 CHNS-O CE instrument). 1H-
and 13C-NMR spectra (CDCl3) were recorded on a Varian Gemini
200 spectrometer operating at 200 MHz and at 50.286 MHz,
respectively. Infrared spectra were measured on a BIO-RAD FTS-
7 FT-IR spectrometer using KBr pellet. Mass spectra (EI) were
acquired with a JEOL JMS-SX102 mass spectrometer.
Co1B-N20B
Co1B-N8B
N1A-Co1A-Cl1A
N1A-Co1A-Cl2A
Cl1A-Co1A-Cl2A
N1A-Co1A-N8A
Cl1A-Co1A-N8A
Z. Anorg. Allg. Chem. 2005, 631, 763Ϫ768
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© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
765

K. Lappalainen, K. Yliheikkilä, A. S. Abu-Surrah, M. Polamo, M. Leskelä, T. Repo
3.2 Synthesis of ligands
3.2.5 2,6-bis[(benzylimino)ethyl]pyridine (BBzEP)
(5)
3.2.1 2,6-bis[(R)-(ϩ)-bornylimino)methyl]pyridine
(BBoMP) (1)
The ligand was prepared following the same procedure described
above (3.2.3).
A solution of 2,6-pyridinedicarboxaldehyde (0.22 g, 1.63 mmol) in
MeOH (15 mL) was added to a solution of (R)-(ϩ)-bornylamine
(0.5 g, 3.26 mmol) in the same solvent (20 mL) and 3 drops of 97 %
formic acid was added. After 4 h of stirring at room temperature,
a white precipitate was formed which was collected, washed with
cold methanol (2ϫ10 ml) and dried in vacuum. Yield: 0.35 g
(52 %), m. p. 141 °C. 1H NMR (CDCl3): δ ϭ 8.82 (s, 2H, CHϭ
N.), 8.12-7.70 (m, 3H, Harom.), 3.53-3.48 (m, 4H, N-CH2-Born.), 0.96
(s, 6H, head), 0.90 (s, 6H, head), 0.71 (s, 6H, Born.). 13C {1H}
NMR (CDCl3): δ ϭ 160.1 (CϭN). IR: ν(cmϪ1) ϭ 1642 m (CϭN).
Anal. Calcd. for C27H39N3: C, 79.95; H, 9.69; N, 10.4. Found: C,
79.36; H, 9.93; N, 10.3 %.
1.46 g (13.7 mmol) of the benzylamine was allowed to react with
0.97 g (5.9 mmol) of 2,6-diacetylpyridine. Yield 1.93 g, (96 %), H
1
NMR (CDCl3): δ ϭ 2.43 (d, 6H, CH3), 4.69 (s, 4H, CH2), 7.13-
7.38 (m, 10H, Harom.), 7.66 (t, 1H, Harom.), 8.14 (d, 2H, Harom.).
13C {1H} NMR (CDCl3): δ ϭ 167.70 (CϭN). IR ν(cmϪ1) ϭ
1638 m (CϭN). Anal. Calcd. for C23H23N3. 0.5 H2O: C 78.83, H
6.90, N 11.99. Found: C 79.24, H 6.50, N 12.43 %.
3.2.6 2,6-bis[(1-naphthylimino)methyl]pyridine
(BNaMP) (6)
A solution of 2,6-pyridinedicarboxaldehyde (1.0 g, 7.4 mmol) in
MeOH (25 mL) was added to a solution of 1-naphthylamine
(2.12 g, 14.8 mmol) in the same solvent (25 mL) and 3 drops of
97 % formic acid was added. After 3 h of stirring at room tempera-
ture, a yellow precipitate was filtered, washed with cold methanol
(2ϫ5 ml) and dried in vacuum. Yield: 2.7 g (93 %), m. p. 172 °C.
1H NMR (CDCl3): δ ϭ 8.81-7.19 (m, 19H, Harom.). 13C {1H} NMR
(CDCl3): δ ϭ 160.45 (CϭN). IR ν(cmϪ1) ϭ 1620 m (CϭN). Anal.
Calcd. for C27H19N3: C, 84.13; H, 4.96; N, 10.9. Found: C, 83.83;
H, 4.86; N, 10.4 %.
3.2.2 2,6-bis[(-)-cis-myrtanylimino)methyl]pyridine
(BMyMP) (2)
A solution of 2,6-pyridinedicarboxaldehyde (0.29 g, 2.15 mmol) in
MeOH (15 mL) was to add a solution of (-)-(cis)-myrtanylamine
(0.72 g, 4.72 mmol) in the same solvent (20 mL) and 3 drops of
97 % formic acid was added. The reaction mixture was stirred at
50 °C for 3 days after which the brown oil product was, washed
with pentane (2ϫ50 ml) and dried in vacuum. Yield: 0.60 g (70 %).
1H NMR (CDCl3): δ ϭ 8.49 (s, 2H, CHϭN). 13C {1H} NMR
(CDCl3): δ ϭ 161.5 (CϭN). IR: ν(cmϪ1) ϭ 1636 m (CϭN). Anal.
Calcd. for C27H39N3: C, 79.95; H, 9.69; N, 10.4. Found: C, 79.53;
H, 9.82; N, 10.2 %.
3.3 Synthesis of complexes
3.3.1 2,6-bis[(R)-(ϩ)-bornylimino)methyl]pyridine
iron(II) chloride (7) and 2,6-bis[(R)-(ϩ)-
bornylimino)methyl]pyridine cobalt(II) chloride (13)
A filtered solution of the ligand 1 0.30 g, (0.74 mmol) in THF
(30 ml) was added to FeCl2 or CoCl2 (0.67 mmol) powder under
continuous stirring at room temperature. Upon addition a precipi-
tate started to form. After 3 h, the solid was filtered, washed with
ether (2ϫ5 mL), n-pentane (2ϫ5 mL) and dried in vacuum. 7,
Yield: 0.22 g (62 %). M.p.(dec) 155 °C. IR: ν [cmϪ1] ϭ 1581 m (Cϭ
N). Anal. Calcd. for C27H39N3FeCl2. 5H2O: C, 59.90; H, 7.44; N,
7.76. Found: C, 59.90; H, 7.42; N, 7.39. 13, Yield: 0.25 g (70 %),
green. M.p. (dec) 207 °C. IR: ν(cmϪ1) ϭ 1582 m (CϭN). Anal.
Calcd. for C27H39N3CoCl2: C, 60.56; H, 7.34; N, 7.85. Found: C,
60.45; H, 7.34; N, 7.28 %. Suitable crystals of compound 13 were
grown from chloroform.
3.2.3 2,6-bis[(cyclohexanemethylimino)ethyl]pyridine
(BChEP) (3)
2,6- Diacetylpyridine (0.92 g, 5.7 mmol) and three drops of formic
acid (97 %) was to added to cyclohexanemethylamine (1.50 g,
13.2 mmol). After two days the reaction mixture was put in vac-
uumat 65 °C for 5 hours to remove excess of amine and water
formed in reaction. Yield 1.91 g (96 %) 1H NMR (CDCl3): δ ϭ
1.00-1.90 (m, 12H, Hcyclohex.), 2.39 (s, 6H, CH3), 3.35 (d, 4H, CH2),
7.69 (t, 1H, Harom.), 8.10 (d, 2H, Harom.). 13C {1H} NMR (CDCl3):
δ ϭ 166.41 (CϭN). IR: ν(cmϪ1) 1635 m (CϭN). Anal. Calcd. for
C23H35N3. 0.5 H2O: C 76.19, H 10.01, N 11.59. Found: C 77.03,
H 10.11, N 11.55 %.
3.3.2 2,6-bis[(-)-cis-myrtanylimino)methyl]pyridine
iron(II) chloride (8) and 2,6-bis[(cis-myrtanylimino)-
methyl]pyridine cobalt(II) chloride (14)
3.2.4 2,6-bis[(benzylimino)methyl]pyridine
(BBzMP) (4)
The complexes were prepared following the same procedure de-
scribed above (3.3.1).
The ligand was prepared following the same procedure described
above (3.2.3).
0.59 g (1.5 mmol) of the ligand 2 was allowed to react with
(1.32 mmol) of FeCl2 or CoCl2. 8, Yield: 0.29 g (41 %), purple.
M.p.(dec) 289 °C. (MS, EI) :m/z (%) 531 (10 %), 496 (10 %), 407
1.63 g (15.2 mmol) of the benzylamine was allowed to react with
0.85 g (6.3 mmol) of 2,6-pyridinedicarboxaldehyde. Yield 1.89 g,
(96 %), 1H NMR (CDCl3): δ ϭ 4.81 (s, 4H, CH2), 7.16-7.29 (m,
10H, Harom.), 7.70 (t, 1H, Harom.), 8.15 (d, 2H, Harom.), 8.45 (s, 2H,
CH). 13C {1H} NMR (CDCl3): δ ϭ 162.61 (CϭN). IR ν(cmϪ1) ϭ
1630 m (CϭN). Anal. calcd. for C21H19N3: C 80.48; H 6.11; N
13.41. Found: C 79.77; H 6.25; N 13.25 %.
(80 %). IR: ν(cmϪ1
) ϭ 1567 m (CϭN). Anal. Calcd. for
C27H39N3FeCl2: C, 60.92; H, 7.38; N, 7.89. Found: C, 60.73; H,
7.02; N, 7.38. 14, Yield: 0.35 g (50 %), green. M.p.(dec) 293 °C. IR:
ν [cmϪ1] ϭ 1587 m (CϭN). Anal. Calcd. for C27H39N3CoCl2: C,
60.56; H, 7.34; N, 7.84. Found: C, 59.15; H, 6.99; N, 6.96 %.
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Z. Anorg. Allg. Chem. 2005, 631, 763Ϫ768

Iron(II)- and Cobalt(II) Complexes with Tridentate Bis(imino)pyridine
Table 2 Crystallographic data parameters for data collection and
refinement for [CoCl2{2,6-bis[R-(ϩ)-(bornylimino)methyl]-
pyridine}] · /2 CHCl3 (13).
3.3.3 2,6-bis[(cyclohexanemethylimino)ethyl]pyridine
iron(II) (9)
1
Solid iron(II) chloride 0.29 g (2.3 mmol) was added to a stirred
solution of ligand 3 1.0 g, (2.9 mmol) in THF (25 ml). Stirring was
continued for 24 hours. Dark blue product was filtered off and
washed with THF (10 ml) and Et2O (10 ml) and dried in vacuum.
Yield: 1.0 g (92 %), blue. (MS,EI): m/z 479. IR: ν [cmϪ1] ϭ 1562 m
(CϭN). Anal. Calcd. for C23H35N3FeCl2: C, 57.52; H, 7.34; N,
8.75. Found: C, 57.42; H, 7.33; N, 8.82 %.
Entry
[CoCl2(BBoMP)] (13)
Chemical formula
Formula weight
T /K
C27H39N3CoCl2·1/2 CHCl3
595.13
173(2)
monoclinic
P21
7.6603(11)
28.3153(14)
13.5365(18)
97.927(9)
2908.1(6)
4
Crystal system
Space group
˚
a /A
˚
b /A
˚
c /A
3.3.4 2,6-bis[(benzylimino)methyl]pyridine iron(II)
(10)
β /°
3
˚
V /A
Z
The complex was prepared following the same procedure described
above (3.3.3).
Dcalc /g cmϪ3
1.359
0.933
0.18 x 0.10 x 0.08
5.02 to 27.52
Absorption coefficient /mmϪ1
Crystal dimensions /mm
θ range /°
0.78 g (2.5 mmol) of the ligand 4 was allowed to react with 0.25 g
(2.0 mmol) of FeCl2. 12, Yield: 0.80 g (91 %), blue. (MS,EI): m/z
Scan mode
Number of data collected
Number of unique data
Number of data refined
Number of parameters
Ra) [I > 2σ(I)]
40410
13134 [Rint ϭ 0.0559]
13134
631
0.0432
0.0769
0.295 and Ϫ0.376
439. IR: ν(cmϪ1
)
ϭ
1585 m (CϭN). Anal. Calcd. for
C21H20N3FeCl2: C, 57.30; H, 4.35; N, 9.55. Found: C, 56.87; H,
4.59; N, 9.25 %.
b)
wR2
Residual density /eAϪ3
3.3.5 2,6-bis[(benzylimino)ethyl]pyridine iron(II) (11)
a) RϭΣʈFoΗ-ΗFcʈ/ΣΗFoΗ.
The complex was prepared following the same procedure described
above (3.3.3).
b) wR2 ϭ [Σ[w(Fo2-Fc2)2]/Σ[w(Fo2)2]]1/2
.
1.1 g (3.1 mmol) of the ligand 5 was allowed to react with 0.31 g
(2.5 mmol) of FeCl2. Yield: 0.9 g (77 %), blue. (MS, EI) :m/z (%)
468 (5 %), 341 (15 %), 250 (80 %). IR: ν(cmϪ1) ϭ 1585 w (CϭN).
Anal. Calcd. for C23H23N3FeCl2: C, 59.00; H, 4.95; N, 8.98. Found:
C, 58.98; H, 5.18; N, 8.10 %.
mation may be obtained free of charge from The Director, CCDC,
12 Union Road, Cambridge, CB2 1EZ UK [Fax. (int code)
ϩ44(1223) 336-033, or e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk.
Acknowledgement. Financial support by the University of Helsinki,
Academy of Finland (grants no. 77317 and 204408) and Finnish
National Technology agency (TEKES) are gratefully acknowl-
edged. K. L. would like to thank MSc Mika Kettunen for fruitful
discussion.
3.3.6 2,6-bis[(1-naphthylimino)methyl]pyridine iron
(II) chloride (12) and 2,6-bis[(1-naphthyl-
imino)methyl]pyridine cobalt (II) chloride (15)
A filtered solution of the ligand 6 (0.50 g, 1.32 mmol) in THF
(50 ml) was added to FeCl2 or CoCl2 (0.15 g 1.2 mmol) powder
under continuous stirring at room temperature. Upon addition a
precipitate started to form gradually. After 18 h, the solid was fil-
tered, washed with THF (2ϫ25 mL), n-pentane (2ϫ25 mL) and
dried in vacuum. 12, Yield: 0.39 g (63 %), dark green. M.p.
References
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(dec) °C. IR: ν(cmϪ1
) ϭ 1585 s (CϭN). Anal. Calcd. for
C27H19N3FeCl2 0.5 H2O: C, 62.21; H, 3.86; N, 8.06. Found: C,
61.93; H, 4.23; N, 7.59. 15, Yield: 0.68 g (68 %), brown. M.p. (dec)
186 °C. IR: ν(cmϪ1
) ϭ 1586 s (CϭN). Anal. Calcd. for
C27H19N3CoCl2. H2O: C, 60.80; H, 3.96; N, 7.87. Found: C, 61.05;
H, 3.99; N, 7.51 %.
[3] L.K. Johnson, C.M. Killian, M. Brookhart, J. Am. Chem. Soc.
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3.4 Crystal structure determination for 13 · 1/2 CHCl3
Crystal data for C27H39Cl2N3Co·1/2 CHCl3 Data were collected on
a Nonius KappaCCD diffractometer. Structure was solved and the
non-hydrogen atoms were refined with full-matrix least-squares on
F2 using SHELXTL 97 program package at T ϭ 173(2) K, λ(Mo
KͰ) ϭ 0.71073 A, and µ(Mo KͰ) ϭ 0.933 mmϪ1. The crystal data,
˚
cell parameters and specific data collection parameters are summa-
rized in table 2. Crystallographic data for the structural analysis
have been deposited with the Cambridge Crystallographic Data
Centre, CCDC no. 229490 for compound 13. Copies of this infor-
Z. Anorg. Allg. Chem. 2005, 631, 763Ϫ768
zaac.wiley-vch.de
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
767

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768
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 763Ϫ768