Activation of chlorobenzene with Ni(O) N,N-chelates - A remarkably profound effect of a minuscule change in ligand structure

Article abstract of DOI:10.1139/v05-022

Activation of the C-Cl bond of chlorbenzene with [(COD)₂Ni] and a bidentate N,N-ligand such as N,N,N′,N′-tetramethylethylenediamine (tmeda) and 2,2′-bipyridyl (bipy) has been reported to produce σ-phenyl complexes [(tmeda)Ni(Ph)Cl] (1) and [(bipy)Ni(Ph)Cl], respectively. However, in sharp contrast, we found that similar reactions involving almost the identical ligands N,N,N′,N′- tetraethylethylenediamine (teeda) and 6,6′-dimethy 1-2,2′-bipyridyl (6,6′-Me₂bipy) resulted in homocoupling and the formation of non-organometallic dichlorocomplexes [(teeda)NiCl₂] and [(6,6′-Me₂bipy)NiCl₂]. The latter two compounds and 1 were characterized by single-crystal X-ray diffraction data. The remarkable change in the reaction outcome points to its extremely high sensitivity to minor alterations in the structure of the stabilizing N,N-ligand. In contrast, analogous reactions of [Pd(dba)₂] with PhI in the presence of teeda or 1,2-dipiperidinoethane (dpe) produced the expected σ-phenyl complexes [(teeda)Pd(Ph)I] and [(dpe)Pd(Ph)I], much like the previously reported reaction with tmeda.

Full text of DOI:10.1139/v05-022

640
Activation of chlorobenzene with Ni(0) N,N-
chelates — A remarkably profound effect of a
minuscule change in ligand structure1
William J. Marshall and Vladimir V. Grushin
Abstract: Activation of the C—Cl bond of chlorbenzene with [(COD)2Ni] and a bidentate N,N-ligand such as
N,N,N′,N′-tetramethylethylenediamine (tmeda) and 2,2′-bipyridyl (bipy) has been reported to produce σ-phenyl com-
plexes [(tmeda)Ni(Ph)Cl] (1) and [(bipy)Ni(Ph)Cl], respectively. However, in sharp contrast, we found that similar reac-
tions involving almost the identical ligands N,N,N′,N′-tetraethylethylenediamine (teeda) and 6,6′-dimethyl-2,2′-
bipyridyl (6,6′-Me2bipy) resulted in homocoupling and the formation of non-organometallic dichlorocomplexes
[(teeda)NiCl2] and [(6,6′-Me2bipy)NiCl2]. The latter two compounds and 1 were characterized by single-crystal X-ray
diffraction data. The remarkable change in the reaction outcome points to its extremely high sensitivity to minor alter-
ations in the structure of the stabilizing N,N-ligand. In contrast, analogous reactions of [Pd(dba)2] with PhI in the pres-
ence of teeda or 1,2-dipiperidinoethane (dpe) produced the expected σ-phenyl complexes [(teeda)Pd(Ph)I] and
[(dpe)Pd(Ph)I], much like the previously reported reaction with tmeda.
Key words: C-Cl activation, zerovalent nickel complexes, N,N-ligands, oxidative addition, homocoupling, X-ray analysis.
Résumé : Il a été rapporté antérieurement que l’activation de la liaison C—Cl du chlorobenzène à l’aide de
[(COD)2Ni] et d’un ligand N,N bidentate, tel la N,N,N′,N′-tétraméthyléthylènediamine (tmeda) ou le 2,2′-bipyridyle
(bipy), conduit à la formation de complexes σ-phényles, tels le [(tmeda)Ni(Ph)Cl] (1) et le [(bipy)Ni(Ph)Cl] respective-
ment. Les observations faites dans ce travail contrastent fortement avec ces résultats alors que des réactions semblables
impliquant les ligands très semblables N,N,N′,N′-tétraéthyléthylènediamine (teeda) et 6,6′-diméthyl-2,2′-bipyridyle
(6,6′-Me2bipy) conduisent à un homocouplage et à la formation des dichlorocomplexes non-organométalliques
[(teeda)NiCl2] et [(6,6′-Me2bipy)NiCl2]. Ces deux derniers complexes et le composé 1 ont été examinés par diffraction
des rayons X sur un cristal unique. Les changements remarquables observés dans les résultats de ces réactions indi-
quent qu’ils sont extrêmement sensibles à des changements mineurs dans la structure du ligand N,N stabilisateur. Au
contraire, les réactions analogues du [Pd(dba)2] avec le PhI en présence de teeda ou de 1,2-dipipéridinoéthane (dpe) ont
conduit aux complexes σ-phényles attendus [(teeda)Pd(Ph)I] et [(dpe)Pd(Ph)I], tel qu’il avait été observé antérieurement
dans les réactions avec le tmeda.
Mots clés : activation de la liaison C-Cl, complexes zérovalent du nickel, ligands N,N, addition oxydante, homocou-
plage, analyse de diffraction des rayons X.
[Traduit par la Rédaction] Marshall and Grushin 645
Introduction
are most often used as catalysts for these reactions. Some
bidentate nitrogen (17) and N-heterocyclic carbene (18–21)
ligands have recently been offered as an alternative to or-
ganic phosphines for Pd catalysis. While in general tertiary
amines are poorly efficient stabilizing ligands in Pd catalysis,
the recently reported Pd(OAc)2–Dabco catalytic system dem-
onstrates high efficiency in Suzuki–Miyaura coupling (22).
Nickel, a metal that is considerably less costly than palla-
dium, is also often used for cross-coupling reactions of
haloarenes. The Ar—X bond is activated by Ni(0) more eas-
ily than by Pd(0), as illustrated by the chemistry of poorly
Catalysis with metal complexes is the primary tool for
solving the problem of the notoriously low reactivity of non-
activated (1, 2) haloarenes toward nucleophiles. Consider-
able progress (3–16) has been made in the development of
catalytic transformations of aryl halides and triflates, Ar–X
(X = Cl, Br, I, OTf), such as Kumada, Suzuki–Miyaura (11),
and Negishi (12) coupling, the Mizoroki–Heck olefin arylation
(13), and various carbonylation, amination (14, 15), and cyan-
ation (16) reactions. Palladium tertiary phosphine complexes
Received 5 October 2004. Published on the NRC Research Press Web site at http://canjchem.nrc.ca on 14 June 2005.
Dedicated to Professor Howard Alper.
W.J. Marshall and V.V. Grushin.2 Central Research and Development, E.I. DuPont de Nemours and Co., Inc.,3 Experimental
Station, Wilmington, DE 19880-0328, USA.
1This article is part of a Special Issue dedicated to Professor Howard Alper.
2Corresponding author (e-mail: vlad.grushin-1@usa.dupont.com).
3Contribution No. 8578.
Can. J. Chem. 83: 640–645 (2005)
doi: 10.1139/V05-022
© 2005 NRC Canada

Marshall and Grushin
641
Fig. 1. An ORTEP drawing of 1 with thermal ellipsoids drawn
to the 50% probability level. Selected bond distances (Å) and an-
gles (°): Ni(1)—C(7) 1.891(2), Ni(1)—N(1) 1.971(1), Ni(1)—
N(2) 2.053(1), Ni(1)—Cl(1) 2.184(1); C(7)-Ni(1)-N(1) 92.61(6),
C(7)-Ni(1)-N(2) 179.33(6), N(1)-Ni(1)-N(2) 86.72(5), C(7)-Ni(1)-
Cl(1) 88.49(5), N(1)-Ni(1)-Cl(1) 178.80(4), N(2)-Ni(1)-Cl(1)
92.17(3).
reactive chloroarenes (6, 23). However, oxidative addition of
the Ar—X bond to Ni(0), the first key step of the catalytic
loop, is often complicated, especially for X = I and Br, by
radical processes (6, 24, 25) and homocoupling, also known
as the Semmelhack reaction (8, 26, 27). We were interested
in the oxidative addition of chloroarenes to Ni(0) stabilized
with diamine ligands, to explore the possibility of using such
systems as catalysts for carbon–heteroatom bond formation.
Results and discussion
In 1987, Wenschuh and Zimmering (28) reported the for-
mation of [(tmeda)Ni(Ph)Cl] (1) (tmeda = N,N,N′,N′-tetra-
methylethylenediamine) in 76% isolated yield upon
oxidative addition of PhCl to [(COD)2Ni] (COD = 1,5-cyclo-
octadiene) in the presence of tmeda at room temperature
(eq. [1]).
N
room temp., 4 h
[1]
[(COD)2Ni] + PhCl + tmeda
Ni
-2COD
Cl
N
1, 76%
No characterization of 1 was presented in the article (28),
although SO2 insertion into the Ni—C bond was later re-
ported by the same group (29). Having prepared orange-
yellow 1 in 70%–89% yield via the Wenschuh–Zimmering
procedure, we attempted characterization of this complex.
The composition of 1 was confirmed by satisfactory C, H, N
microanalysis data. It was found that 1 is insoluble in al-
kanes, benzene, toluene, and ether, and slightly soluble in
THF (28). Although 1 is easily soluble in CH2Cl2 and 1,2-
dichloroethane (dce), these chlorinated solvents decompose
1 even at room temperature within a few minutes (CH2Cl2)
above) Ni(II) complex. In accord with trans-influence
considerations, the Ni—N bond trans to Ph (2.053(1) Å) is
longer than that trans to Cl (1.971(1) Å). The aromatic ring
is orthogonal to the coordination plane of the complex, as in
the closely related structure [(tmeda)Pd(Ph)I] (30).
The aforementioned decomposition of 1 in chlorinated
solvents was found to produce pale green crystals, which we
identified by X-ray analysis as [(tmeda)3Ni3(µ-Cl)3(µ3-
Cl)(µ3-OH)]+Cl– whose X-ray structure has been reported
previously (31, 32). Because 1 was handled under rigorously
anhydrous conditions, the source of OH for the trinuclear
complex was probably the surface of the glass.
Although the structure of 1 was established, the complex
was of limited further use for stoichiometric and catalytic
studies because of its poor solubility. It was then reasoned
that the teeda analogue of 1 ([(teeda)Ni(Ph)Cl], teeda =
N,N,N′,N′-tetraethylethylenediamnie), should be more
readily soluble in organic solvents and hence suitable for
further studies. Indeed, the closely related Pd complexes
[(teeda)Pd(Ph)I] and [(dpe)Pd(Ph)I] (dpe = 1,2-dipiperidino-
ethane) were prepared (eq. [2]) by the procedure reported
(30) for [(tmeda)Pd(Ph)I] and were found to be more soluble
than the latter.
1
or several hours (dce). We succeeded in obtaining H and
1
13C NMR data for 1 in dce-d4. At room temperature, the H
NMR spectrum of 1 exhibited three sharp aromatic reso-
nances at 6.6 (1H, p-Ph), 6.7 (2H, m-Ph), and 7.5 (2H, o-Ph)
ppm along with a broadened multiplet at 2.0–2.7 ppm from
the aliphatic protons. The 13C NMR spectrum recorded at
20 °C displayed two signals from the methyl groups (47.1
and 49.3 ppm), two methylene resonances (56.9 and 61.1 ppm),
and four aromatic peaks (121.4, 124.5, 136.8, and
147.5 ppm). The aromatic lines were sharp, whereas consid-
erable line broadening (∆ν1/2 = 15–20 Hz) was observed for
the methyl and methylene resonances. The latter sharpened
to ∆ν1/2 = 10 Hz upon cooling to 10 °C, indicating that some
exchange processes were occurring. Although studying these
dynamic processes was beyond the scope of our work, the
ambient temperature NMR spectra were fully consistent
with the structural formula of 1 as shown in eq. [1].
X-ray quality crystals of 1 were obtained from dce–hex-
anes. Two polymorphic crystalline forms of 1 were observed,
thin needles (major) and irregular blocks (minor). Both
forms were analyzed by X-ray diffraction. The structure of 1
determined for the thin needle polymorph (C2/c, a =
22.96(2) Å, b = 7.828(8) Å, c = 16.56(1) Å, β = 115.04(4)°)
was of poor quality due to its small crystal size. A good
quality X-ray structure of 1 (Fig. 1) was obtained for one of
the irregular block crystallites. The molecule of 1 is square-
planar, as expected from a diamagnetic (see the NMR data
R
R
R
R
N
N
benzene, 50 o
-dba
C
N
N
[2]
[Pd2(dba)3] + PhI +
Pd
I
R
R
R
R
R
R
R
R
N
N
N
N
N
or
=
N
© 2005 NRC Canada

642
Can. J. Chem. Vol. 83, 2005
Fig. 2. An ORTEP drawing of [(teeda)NiCl2] with thermal ellip-
soids drawn to the 50% probability level. Selected bond dis-
tances (Å) and angles (°): Ni(1)—N(1) 2.050(2), Ni(1)—N(2)
2.059(2), Ni(1)—Cl(1) 2.232(1), Ni(1)—Cl(2) 2.232(1); N(1)-
Ni(1)-N(2) 89.32(6), N(1)-Ni(1)-Cl(1) 107.12(4), N(2)-Ni(1)-
Cl(1) 110.87(5), N(1)-Ni(1)-Cl(2) 110.60(5), N(2)-Ni(1)-Cl(2)
106.14(4), Cl(1)-Ni(1)-Cl(2) 126.50(2).
Surprisingly, however, the reaction of [(COD)2Ni] with
PhCl in the presence of teeda did not afford
[(teeda)Ni(Ph)Cl], but rather Semmelhack-type coupling oc-
curred to produce deep-purple, paramagnetic [(teeda)NiCl2]
(eq. [3]).
N
room temp.
-2COD
Cl
Cl
[3]
[(COD)2Ni] + PhCl + teeda
Ni
+
Ph-Ph
N
The structure of the complex [(teeda)NiCl2] was estab-
lished by X-ray analysis, showing tetrahedral coordination
geometry around Ni (Fig. 2). In accord with the tetrahedral
structure, two broad lines at 7.5 and 11.9 ppm were observed
1
in the H NMR spectrum of paramagnetic [(teeda)NiCl2] in
benzene-d6.
Considering the minor change in the structures of tmeda
and teeda, the difference in the outcomes of the two reac-
tions (eqs. [1] and [3]) is remarkable. The tmeda vs. teeda
case, however, is not unique. While it has been reported (28)
that the reaction of [(COD)2Ni] with 2,2′-bipyridyl (bipy)
and PhCl leads to a nickel aryl ([(bipy)Ni(Ph)Cl]), we found
that 6,6′-dimethyl-2,2′-bipyridyl (6,6′-Me2bipy) produces the
paramagnetic inorganic dichloride [(6,6′-Me2bipy)NiCl2]
under similar conditions (eq. [4] and Fig. 3). No N-chelated
Ni complexes were formed when [(COD)2Ni] was reacted
with PhCl and N,N,N′,N′-tetraisopropylethylenediamine (tipeda).
Considering the well-known low nucleophilicity of sterically
hindered Hunig’s base (i-Pr2NEt), this observation is not sur-
prising. Nonetheless, a simple high-yield preparation of
tipeda is presented in the Experimental section.
Fig. 3. An ORTEP drawing of [(6,6′-Me2bipy)NiCl2] with ther-
mal ellipsoids drawn to the 50% probability level. Selected bond
distances (Å) and angles (°): Ni(1)—N(1) 1.985(1), Ni(1)—
N(1A) 1.985(1), Ni(1)—Cl(2) 2.211(1), Ni(1)—Cl(1) 2.218(1);
N(1)-Ni(1)-N(1A) 82.76(7), N(1)-Ni(1)-Cl(2) 109.05(4), N(1A)-
Ni(1)-Cl(2) 109.05(4), N(1)-Ni(1)-Cl(1) 105.80(4), N(1A)-Ni(1)-
Cl(1) 105.81(4), Cl(2)-Ni(1)-Cl(1) 132.93(3).
N
N
N
Cl
Cl
[(COD)2Ni]
+
PhCl
bipy
6,6'-Me2bipy
-COD, -Ph2
[4]
Ni
Ni
N
-COD
Cl
ref. 28
this work
At this point, it is unclear if the change in the reaction
paths when going from tmeda to teeda or from bipy to 6,6′-
Me2bipy is largely due to electronic or steric (33) factors, or
a combination of both. While considerable progress has been
made in understanding the mechanisms of Semmelhack
homocoupling of aryl halides (25, 27, 34), the results re-
ported by different groups are not completely without con-
troversy (34). The first step of the process is oxidative
addition of Ar–X to Ni(0) to produce an aryl Ni(II) halide
complex. Since chloroarenes are known to be almost
unreactive toward [(COD)2Ni] (26), a bidentate N-ligand
should displace at least one COD in [(COD)2Ni] before oxi-
dative addition of PhCl can occur. As described by Tsou and
Kochi (25) and discussed, most recently, in detail in an ex-
cellent review by Nelson and Crouch (34), an intermediate
Ni(III) aryl species might play a key role in the homo-
coupling reaction. Aryl transfer from Ar–Ni(III) to Ar–Ni(II),
possibly via a bridging intermediate, would produce a diaryl
Ni(III) species that leads to biaryl upon C–C reductive elimi-
nation. Such Ar–Ni(III) species are more likely to emerge
when more electron-rich teeda (vs. tmeda) and 6,6′-Me2bipy
(vs. bipy) are employed. On the other hand, one may not
rule out the solubility factor, i.e., it is conceivable that the
poorly soluble tmeda derivative 1 precipitates out immedi-
ately upon formation, whereas its more soluble teeda ana-
logue may undergo further transformations in solution.
In conclusion, we have demonstrated that Ph–Cl activa-
tion by Ni(0) stabilized with N-chelating ligands does not
© 2005 NRC Canada

Marshall and Grushin
643
necessarily form a σ-phenyl Ni species as the final product,
but can also result in homocoupling and formation of the
corresponding dichloro complex. The outcome of such reac-
tions is remarkably sensitive to even small changes in the
structure of the stabilizing N,N-ligand, as illustrated by the
differing behavior of the tmeda and teeda systems. These
observations might be important for the design of reactions
of haloarenes, catalyzed by Ni N,N-chelate complexes.
Preparation of [(dpe)Pd(Ph)I]
Under N2, a stirring mixture of Pd(dba)2 (1.00 g), dpe
(0.44 g), iodobenzene (0.51 g), and benzene (25 mL) was
slowly heated to 50 °C and kept at that temperature for
15 min. The greenish reaction mixture was filtered through
Celite®, which was then washed with benzene (2 × 10 mL).
After the combined filtrate and washings were evaporated,
the residue was washed with ether (3 × 10 mL) to remove
dba. Recrystallization of the residue from dichloromethane–
ether produced 0.40 g (46%) of [(dpe)Pd(Ph)I] as “copper”
1
orange flakes. H NMR (dichloromethane-d2, 20 °C) δ: 1.0–
Experimental
1.8 (m, CH2), 2.7–3.1 (m, CH2), 3.8 (m, CH2), 6.8 (m, 1H,
p-Ph), 6.9 (m, 2H, m-Ph), 7.3 (m, 2H, o-Ph). Anal. calcd. for
C18H29IN2Pd (%): C 42.7, H 5.8, N 5.5; found: C 42.3, H
5.7, N 5.4.
Materials and instruments
All manipulations with Ni complexes were conducted in a
glovebox under N2. All chemicals were purchased from
Aldrich, Acros Organics, and Strem Chemical Companies.
The diamines were distilled from CaH2 under N2 prior to
use. Both [(COD)2Ni] and 6,6′-Me2bipy were used as re-
ceived. All solvents were purified and (or) dried by standard
techniques and stored over freshly activated molecular sieves
(4 Å) in the glovebox. NMR spectra were obtained with
Bruker Avance DPX 300 and DRX 400 instruments. A
Bruker Smart 1 K CCD system was used for single crystal
X-ray diffraction studies. Microanalyses were performed by
Micro-Analysis, Inc., Wilmington, Delaware, USA.
Preparation of [(teeda)NiCl2]
A solution of teeda (1.00 g) in chlorobenzene (2 mL) was
added to [(COD)2Ni] (1.22 g), and the mixture was stirred at
room temperature overnight. Hexanes (8 mL) were added.
After 30 min, the deep-purple solid was separated by filtra-
tion, washed with hexanes (4 × 10 mL), and dried under vac-
uum. The yield was 0.89 g (66%). Anal. calcd. for
C10H24Cl2N2Ni (%): C 39.8, H 8.0, N 9.3; found: C 39.8, H
7.3, N 9.2. X-ray quality crystals were grown from dichloro-
methane–hexanes.
Preparation of [(6,6′-Me2bipy)NiCl2]
Synthesis of [(tmeda)Ni(Ph)Cl] (1)
A mixture of 6,6′-Me2bipy (0.50 g), [(COD)2Ni] (0.70 g),
and chlorobenzene (6 mL) was stirred at room temperature
for 1 day. A green color emerged immediately upon mixing
the reagents, which then turned dark-blue within seconds,
and finally light-purple. The light-purple solid was separated
by filtration, washed with chlorobenzene (2 × 2 mL) and
hexanes (2 × 3 mL), and dried under vacuum. The yield was
0.79 g (99%). Anal. calcd. for C12H12Cl2N2Ni (%): C 45.9,
H 3.8, N 8.9; found: C 46.0, H 3.7, N 8.7. X-ray quality
crystals were grown from hot 1,2-dichloroethane.
A slight modification of the reported procedure (28) was
used. A solution of tmeda (0.28 mL) in chlorobenzene
(2 mL) was added to [(COD)2Ni] (0.42 g), and the mixture
was stirred at room temperature for 6 h. Hexanes (10 mL)
were added and the mixture was left at room temperature
overnight. The orange-yellow precipitate was separated by
filtration, thoroughly washed with hexanes, and dried under
1
vacuum. The yield of 1 was 0.39 g (89%). H NMR (1,2-
dichloroethane-d4, 20 °C) δ: 2.0–2.7 (m, 16H, CH3 and
CH2), 6.6 (1H, p-Ph), 6.7 (2H, m-Ph), 7.5 (2H, o-Ph). 13C
NMR (1,2-dichloroethane-d4, 20 °C) δ: 47.1 (br), 49.3 (br),
56.9 (br), 61.1 (br), 121.4, 124.5, 136.8, 147.5. Anal. calcd.
for C12H21ClN2Ni (%): C 50.1, H 7.4, N 9.7; found: C 49.9,
H 7.0, N 9.7.
Synthesis of N,N,N′,N′-tetraisopropylethylenediamine
(tipeda)
In air, a mixture of 2-iodopropane (20 mL), ethylene-
diamine (1.1 mL), and potassium carbonate (9.2 g) was stirred
under reflux for 58 h. The tan liquid phase was separated
from the solids, which were then thoroughly washed with
ether (10 × 5 mL). The mother liquor and the washings were
combined, evaporated, and the residue distilled under vac-
uum (86–98 °C at 9.5 mm Hg, (1 mm Hg = 133.322 4 Pa) to
Preparation of [(teeda)Pd(Ph)I]
Under N2, a stirring mixture of Pd(dba)2 (1.00 g), teeda
(0.39 g), iodobenzene (0.51 g), and benzene (25 mL) was
slowly heated to 50 °C and kept at that temperature for
15 min. The greenish reaction mixture was filtered through
Celite®, which was then washed with benzene (2 × 10 mL).
After the combined filtrate and washings were evaporated,
the residue was washed with ether (3 × 10 mL) to remove
dba. Recrystallization of the orange residue from dichloro-
methane–ether produced 0.30 g (36%) of [(teeda)Pd(Ph)I] as
1
produce 3.32 g (87%) of spectroscopically pure tipeda. H
NMR (benzene-d6, 20 °C) δ: 1.1 (t, J = 6.6 Hz, 24H, CH3),
2.7 (s, 4H, CH2), 3.1 (heptet, J = 6.6 Hz, 4H, CH). 13C NMR
(benzene-d6, 20 °C) δ: 21.4, 48.1, 49.4.
Crystallographic studies
1
a pale yellow crystalline solid. H NMR (dichloromethane-
All crystallographic data were collected using a Bruker
Smart 1 K CCD system equipped with Mo Kα radiation at
–100 °C. The structures were solved using direct methods
and refined with the SHELXTL program suite (35). Scatter-
ing factors were obtained from the International Tables for
X-ray Crystallography (36). Additional data and refinement
d2, 20 °C) δ: 1.4 (t, J = 7.1 Hz, 6H, CH3), 1.5 (t, J = 7.1 Hz,
6H, CH3), 2.7 (m, 6H, CH2), 2.8 (m, 2H, CH2), 3.0 (m, 2H,
CH2), 3.2 (m, 2H, CH2), 6.7 (m, 1H, p-Ph), 6.9 (m, 2H, m-
Ph), 7.3 (m, 2H, o-Ph). Anal. calcd. for C16H29IN2Pd (%): C
39.8, H 6.0, N 5.8; found: C 39.7, H 6.0, N 5.7.
© 2005 NRC Canada

644
Can. J. Chem. Vol. 83, 2005
Table 1. Crystallographic data for [(tmeda)Ni(Ph)Cl] (1), [(teeda)NiCl2], and [(6,6′-Me2bipy)NiCl2].
[(tmeda)Ni(Ph)Cl] (1)
[(teeda)NiCl2]
C10H24Cl2N2Ni
[(6,6′-Me2bipy)NiCl2]
Empirical formula
C12H21ClN2Ni
C12H12Cl2N2Ni
FW
287.47
301.92
313.85
Crystal color, form
Crystal system
Space group
Unit cell dimensions
a (Å)
Gold, plate
Monoclinic
P2(1)/c
Purple, irreg. block
Orthorhombic
Pna2(1)
Red-orange, irreg. block
Orthorhombic
Pnma
11.0284(4)
14.7179(14)
14.594(2)
b (Å)
12.2967(5)
12.3740(12)
11.1805(15)
c (Å)
11.4778(4)
7.7454(7)
7.8560(11)
α (°)
90
90
90
90
90
90
90
β (°)
118.629(1)
90
1 366.24(9)
γ (°)
V (Å3)
1 410.6(2)
1 281.9(3)
Z
4
4
4
Density (g cm–3)
Abs. µ (mm–1)
F(000)
1.398
1.592
608
1.422
1.728
640
1.626
1.907
640
Crystal size (mm3)
Temp (°C)
Scan mode
Detector
0.22 × 0.08 × 0.04
–100
ω
Bruker CCD
28.3
0.45 × 0.42 × 0.24
–100
ω
Bruker CCD
28.26
0.35 × 0.35 × 0.32
–100
ω
Bruker CCD
28.29
θmax (°)
No. obsrvd. reflections
No. uniq. reflections
Rmerge
10 437
3 392
0.0251
7 106
2 146
0.0173
10 052
1 589
0.0258
No. of parameters
Sa
149
0.989
141
1.071
83
1.003
R indices [I > 2σ(I)]b
wR2 = 0.0590, R1 = 0.0244
wR2 = 0.0446, R1 = 0.0178
wR2 = 0.0639, R1 = 0.0238
R indices (all data)b
Max diff. peak, hole (e Å–3)
wR2 = 0.0618, R1 = 0.0330
wR2 = 0.0456, R1 = 0.0189
wR2 = 0.0664, R1 = 0.0272
0.358, –0.236
0.201, –0.239
0.383, –0.240
2
aGoF = S = {∑[w(Fo – Fc2)2]/(n – p)}1/2, where n is the number of reflections and p is the total number of refined parameters.
2
2
bR1 = ∑(|Fo| – |Fc|)/∑ |Fo|, wR2 = {∑w(Fo – Fc2)2]/∑w[(Fo )2]}1/2 (sometimes denoted as Rw2).
7. G. Poli, G. Giambastiani, and A. Heumann. Tetrahedron, 56,
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4 Supplementary data for this article are available on the Web site or may be purchased from the Depository of Unpublished Data, Document
Delivery, CISTI, National Research Council Canada, Ottawa, ON K1A 0S2, Canada. DUD 3677. For more information on obtaining mate-
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