Synthesis and structural characterization of η3-allyl (α-diimine)nickel(II) complexes bearing trimethylsilyl groups

Article abstract of DOI:10.1016/j.jorganchem.2004.01.003

A set of isomeric para- and meta-trimethylsilylphenyl ortho -substituted N, N-phenyl α-diimine ligands [(Ar-N=C(Me) -(Me)C=N-Ar) Ar=2,6-di(4-trimethylsilylphenyl)phenyl (16); Ar=2,6-di(3-trimethylsilylphenyl)phenyl (17)] have been synthesized through a two-step procedure. The palladium-catalysed cross-coupling reaction between 2,6-dibromophenylamine (7) and 4-trimethylsilylphenylboronic acid (8), 3-trimethylsilylphenylboronic acid (9) was used to prepare 4,4′-bis(trimethylsilyl) -[1,1′;3′,1″]terphenyl-2 ′-ylamine (10) and 3,3′-bis (trimethylsilyl)-[1,1′;3′, 1″] terphenyl-2′-ylamine (11). The di-1-adamantylphosphine oxide Ad₂P(O)H (13) and di-tert-butyl-trimethylsilylanylmethylphosphine tert-Bu₂ P-CH₂-SiMe₃ (14) were used for the first time as ligands for the Suzuki coupling. The condensation of 2,2,3,3-tetramethoxybutane (15) with anilines 10 and 11 afforded α-diimines 16 and 17. The reaction of π-allylnickel chloride dimer (18), α-diimines (16), (17) and sodium tetrakis[3,5-bis (trifluoromethyl)phenyl]borate (BAF) (19) or silver hexafluoroantimonate (20) led to two sets of isomeric complexes [η³-allyl (Ar-N=C(Me)-(Me)C=N-Ar)Ni]⁺ X^-, [Ar=2,6-di(4-trimethylsilylphenyl)phenyl, X=BAF (3), X=SbF₆ (4); Ar=2,6-di(3-trimethylsilylphenyl)phenyl, X=BAF (5), X=SbF₆ (6)]. The steric repulsion of closely positioned trimethylsilyl groups in 4 caused the distortion of the nickel square planar coordination by 17.6° according to X-ray analysis.

Full text of DOI:10.1016/j.jorganchem.2004.01.003

Journal of Organometallic Chemistry 689 (2004) 1057–1063
www.elsevier.com/locate/jorganchem
Synthesis and structural characterization of
g3-allyl(a-diimine)nickel(II) complexes bearing trimethylsilyl groups
Alex S. Ionkin ,1, William J. Marshall
*
DuPont Central Research & Development, Experimental Station, Wilmington, DE 19880-0328, USA
Received 12 December 2003; accepted 13 January 2004
Abstract
A set of isomeric para- and meta-trimethylsilylphenyl ortho-substituted N,N-phenyl a-diimine ligands [(Ar–N@C(Me)–
(Me)C@N–Ar) Ar ¼ 2,6-di(4-trimethylsilylphenyl)phenyl (16); Ar ¼ 2,6-di(3-trimethylsilylphenyl)phenyl (17)] have been synthesized
through a two-step procedure. The palladium-catalysed cross-coupling reaction between 2,6-dibromophenylamine (7) and 4-tri-
methylsilylphenylboronic acid (8), 3-trimethylsilylphenylboronic acid (9) was used to prepare 4,40-bis(trimethylsilyl)-[1,10;30,100]ter-
phenyl-20-ylamine (10) and 3,30-bis(trimethylsilyl)-[1,10;30,100]terphenyl-20-ylamine (11). The di-1-adamantylphosphine oxide
Ad2P(O)H (13) and di-tert-butyl-trimethylsilylanylmethylphosphine tert-Bu2P-CH2-SiMe3 (14) were used for the first time as li-
gands for the Suzuki coupling. The condensation of 2,2,3,3-tetramethoxybutane (15) with anilines 10 and 11 afforded a-diimines 16
and 17. The reaction of p-allylnickel chloride dimer (18), a-diimines (16), (17) and sodium tetrakis[3,5-bis(trifluoromethyl)phen-
yl]borate (BAF) (19) or silver hexafluoroantimonate (20) led to two sets of isomeric complexes [g3-allyl(Ar–N@C(Me)–(Me)C@N–
Ar)Ni]þ Xꢀ, [Ar ¼ 2,6-di(4-trimethylsilylphenyl)phenyl, X ¼ BAF (3), X ¼ SbF6 (4); Ar ¼ 2,6-di(3-trimethylsilylphenyl)phenyl,
X ¼ BAF (5), X ¼ SbF6 (6)]. The steric repulsion of closely positioned trimethylsilyl groups in 4 caused the distortion of the nickel
square planar coordination by 17.6° according to X-ray analysis.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Nickel; Palladium; Boron; Antimony; a-Diimine; X-ray analysis
1. Introduction
The easily varied steric and electronic properties of
the a-diimine ligands are important features of nickel a-
diimine catalyst systems (trademarked the VersipolÒ
catalyst system by DuPont) for the polymerization of
ethylene, a-olefins and the copolymerization of nonpo-
lar olefins with a variety of functionalized olefins [1]. For
example, the key to producing ultrahigh molecular
weight polymers is the incorporation of phenyl substit-
uents in the ortho-positions of aryl rings for the complex
The corresponding nickel(II) dibromide complex 2
1 [2,3] depicted below:
with para-tert-butylphenyl shows remarkably high po-
lymerisation activity and affords high molecular weight
polyethylene. Further substitution of ortho-phenyl
groups with bulky substituents, e.g. trimethylsilyl, is
expected to affect important catalyst properties such as
catalyst lifetime.
We now report the synthesis of such complexes and
have determined the structures of 3–6 below:
* Corresponding author. Tel.: +302-6952968; fax: +302-6958281.
E-mail address: alex.s.ionkin@usa.dupont.com (A.S. Ionkin).
1
This is DuPont contribution #8415.
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.01.003

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A.S. Ionkin, W.J. Marshall / Journal of Organometallic Chemistry 689 (2004) 1057–1063
Isomeric para- and meta-trimethylsilylphenyl ortho-
substituted N,N-phenyl a-diimine ligands were synthes-
ised. The trimethylsilyl group was chosen to provide
bulk in the axial sites of square planar nickel complexes
and retard the rate of chain transfer [4]. The point where
this steric bulk can be the most effective is in the para-
positions of the ortho-phenyl groups as in complexes 3
and 4. In order to compare polymerization activity, the
meta-trimethylsilyl isomers 5 and 6 were synthesised.
Complexes 5 and 6 should afford substantially less steric
protection for nickel above and below the square plane.
However, the meta-isomers 5 and 6 should be similar to
para-isomers 3 and 4 for other properties like solubility,
overall bulk, etc.
oxane as solvent. To our knowledge, di-1-adamantyl-
phosphine oxide (13) [5] and di-tert-butyl-trimethyl-
silylanylmethylphosphine (14) [6] have not previously
been used as ligands for palladium-catalysed Suzuki
cross-coupling reactions.
The condensation of 2,2,3,3-tetramethoxybutane (15)
[7] with anilines 10 and 11 in the presence of an
acidic catalyst led to the desired a-diimines 16 and 17
(Scheme 2).
The application of a-diketal 15 instead of 2,3-but-
andione [2] resulted in shorter reaction times for the
condensation reactions to a-diimines 16 and 17 [8].
The structures of 16 and 17 were determined by X-ray
analysis. Figs. 1 and 2 show thermal ellipsoid drawings
of the two isomeric molecules 16 and 17. The a-diimine
cores of the isomeric molecules have essentially identical
C–N bond lengths and angles. The different positions
for the trimethylsilyl groups change the dihedral angles
of the phenyl rings relative to each other.
2. Results and discussion
2.1. Synthesis and structural studies of para- and meta-
trimethylsilylphenyl ortho-substituted N,N-phenyl a-
diimines (16), (17)
Table 1 summarizes the bonding parameters for the
a-diimine cores as well as the angles between the mean
planes of the phenyl groups.
The palladium-catalysed Suzuki cross-coupling
reaction between 2,6-dibromophenylamine (7) and 4-
trimethylsilylphenylboronic acid (8) or 3-trimethylsilyl-
phenylboronic acid (9) was used to prepare 4,40-bis
(trimethylsilyl)-[1,10;30,100]terphenyl-20-ylamine (10) and
3,30-bis(trimethylsilyl)-[1,10;30,100]terphenyl-20-ylamine
(11) correspondingly (Scheme 1).
The synthetic protocol involves di-1-adamantyl-
phosphine oxide 13/Pd2dba3 and di-tert-butyl-tri-
methylsilylanylmethylphosphine 14/Pd2dba3 as the
catalysts in the presence of cesium carbonate in 1,4-di-
2.2. Synthesis and structural studies of para- and meta-
trimethylsilylphenyl ortho-substituted N,N-phenyl a-dii-
mine nickel complexes (3)–(6)
The reaction between p-allylnickel chloride dimer 18
[9], a-diimines 16, 17, and sodium tetrakis[3,5-bis(tri-
fluoromethyl)phenyl]borate (BAF) (19) or silver hexa-
fluoroantimonate (20) led to g3-allyl(a-diimine)nickel
complexes 3–6 (Scheme 3).
Scheme 1.

A.S. Ionkin, W.J. Marshall / Journal of Organometallic Chemistry 689 (2004) 1057–1063
1059
Scheme 2.
Fig. 2. ORTEP drawing of a-diimine 17. Thermal ellipsoids are drawn
to the 50% probability level.
nickelsquareplanarcoordinationhasbeendistorted. This
distortion can be measured by the dihedral angle R be-
tween the two sets of planes defined by N1–Ni–N2 and C–
5–Ni–C7. The tetrahedral twist angle for 4 was
17.6°(Fig. 3).
The ORTEP drawing of the meta-isomer 6 revealed
the usual square planar distortion of g3-allyl nickel
fragments. In previous work, this has been shown to
vary from 1.7° to 9.7° [10–12]. In contrast to complex 4,
the tetrahedral twist angle for 6 was 11.3°, which is only
slightly greater than the usual range (Fig. 4).
Fig. 1. ORTEP drawing of a-diimine ligand 16. Thermal ellipsoids are
drawn to the 50% probability level.
While the reaction of p-allylnickel chloride dimer 18
and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]bo-
rate 19 or silver hexafluoroantimonate 20 afforded
complexes 3–6, we were unable to isolate the corre-
sponding complexes from the reaction of bulky ligands
16, 17 with (DME)NiBr2. However, nickel(II) acetyl-
acetonate reacts to give the corresponding diimine
complexes [3]. The hexafluoroantimonate derivatives 4
and 6 afforded single crystals suitable for X-ray analysis
from toluene solutions (Tables 2 and 3).
3. Summary
X-ray analysis of the complexes 4 and 6 reveals that the
central nickel atoms are four-coordinate with the bi-
dentate a-diimine and p-allyl ligands. The position of the
tri- methylsilyl group on the ortho-phenyl moiety has a
substantial effect on the metal coordination geometry.
The ORTEP drawing of 4 (Fig. 3) clearly shows that the
Sterically hindered g3-allyl(a-diimine)Ni complexes
3–6 with distorted configurations bearing 2,6-di(4-
trimethylsilylphenyl)aniline fragments and 2,6-di(3-
trimethylsilylphenyl)aniline fragments have been
prepared. The repulsive interaction of trimethylsi-
lyl groups in the para-position of ortho-substituted

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A.S. Ionkin, W.J. Marshall / Journal of Organometallic Chemistry 689 (2004) 1057–1063
Table 1
ꢀ
Selected bond lengths (A), angles (°) and interplanar angles (°) for 16 and 17
16
17
N1–C1
N2–C2
N1–C5
N2–C29
C1–C2
C1–C3
C2–C4
1.268(3)
1.272(3)
1.415(3)
1.418(3)
1.503(3)
1.500(3)
1.497(3)
N1–C1
N1–C3
1.271(6)
1.424(6)
C1–C1a
C1–C2
1.500(9)
1.480(6)
C29–N2–C2
N2–C2–C1
C5–N1–C1
N1–C1–C2
121.9(2)
C3–N1–C1
119.1(4)
116.1(2)
124.0(2)
115.4(2)
N1–C1–C1a
116.4(5)
(C5–C10)–(N1,C3,N2)
(C5–C10)–(C11–C16)
(C5–C10)–(C20–C25)
(C29–C34)–(N1,C3,N2)
(C29–C34)–(C35–C40)
(C29–C34)–(C44–C49)
62.4
82.6
47.9
64.4
70.2
54.8
(C3–C8)–(N1,C1,C2)
(C3–C8)–(C9–C14)
(C3–C8)–(C18–C23)
88.3
52.0
50.6
Symmetrically redundant values are not included for 17.
Scheme 3.
N,N-phenyl a-diimine ligands of nickel complexes dis-
torts the square planar coordination of the metal center.
Complexes 3–6 catalyze ethylene polymerization. The
polymerization results will be published in due course.
Table 2
Selected bond lengths (A) and angles (°) for 4 and 6
ꢀ
4
6
Bond lengths
Ni1–N1
Ni1–N2
Ni1–C6
Ni1–C7
N1–C1
1.911(4)
1.916(4)
2.035(10)
2.027(5)
1.335(7)
1.339(7)
1.437(6)
1.459(6)
1.423(10)
1.519(8)
1.509(9)
Ni1–N1
Ni1–N2
Ni1–C3
Ni1–C5
N1–C1
N2–C2
N1–C6
N2–C30
C1–C2
C1–C10
C2–C20
1.949(2)
1.949(2)
2.031(3)
2.006(3)
1.299(3)
1.297(3)
1.444(3)
1.448(3)
1.506(3)
1.495(3)
1.484(3)
4. Experimental
4.1. General procedures
N2–C2
N1–C8
All the operations related to catalysts were carried
out under an argon atmosphere using standard Schlenk
techniques. Anhydrous solvents were used in the reac-
tions. Solvents were distilled from drying agents or
passed through alumina columns under an argon or
nitrogen atmosphere. 2,6-Dibromophenylamine, 4-
trimethylsilylphenylboronic acid, 3-trimethylsilylphenyl-
boronic acid, Pd2dba3, silver hexafluoroantimonate
were purchased from Aldrich. Sodium tetrakis[3,5-
bis(trifluoromethyl)phenyl]borate (NaBAF) was pur-
chased from Boulder Scientific.
N2–C32
C1–C2
C1–C3
C2–C4
Bond angles
N1–Ni1–N2
N1–Ni1–C7
N1–Ni1–C5
N2–Ni1–C5
N2–Ni1–C7
C5–Ni1–C7
84.46(17)
100.8(2)
167.0(2)
100.7(2)
168.9(2)
42.7(5)
N1–Ni1–N2
N1–Ni1–C3
N1–Ni1–C5
N2–Ni1–C5
N2–Ni1–C3
C3–Ni1–C5
83.51(9)
103.52(11)
174.85(11)
100.47(11)
168.20(10)
73.13(12)

A.S. Ionkin, W.J. Marshall / Journal of Organometallic Chemistry 689 (2004) 1057–1063
1061
Table 3
Summary of crystal data, data collection, and structure refinement parameters
4
6
16
17
Empirical formula
Formula weight
Crystal color, form
Crystal system
C69H85F6N2NiSbSi4
1349.21
C62H77F6N2NiSbSi4
1257.08
C52H64N2Si4
829.41
C52H64N2Si4
829.41
Dark red prism
Triclinic
Red block
Monoclinic
P21=c
17.623(5)
17.558(5)
20.688(5)
Colorless plate
Triclinic
Colorless prism
Monoclinic
P21=n
10.3291(11)
13.1990(12)
18.924(2)
ꢁ
ꢁ
Space group
ꢀ
P1
P1
a (A)
ꢀ
11.220(3)
13.848(4)
24.210(7)
76.971(5)
78.851(5)
78.395(6)
3546.4(17)
2
11.760(6)
13.277(7)
16.711(8)
79.783(9)
88.419(10)
88.016(10)
2566(2)
b (A)
ꢀ
c (A)
a (°)
b (°)
c (°)
101.39(4)
98.899(3)
3
ꢀ
V (A )
6275(3)
4
1.331
2548.9(4)
2
1.081 mg
Z
2
1.074
Density (g/cm3)
1.263
0.77(k ¼ Mo)
1404
Absolute l (mmꢀ1
F ð000Þ
)
0.81(k ¼ 0:7100)
2608
0.15(k ¼ Mo)
892
0.15mm(k ¼ Mo)
892
Crystal size (mm)
Scan mode
Detector
0.34 ꢁ 0.07 ꢁ 0.07
0.03 ꢁ 0.03 ꢁ 0.01
0.42 ꢁ 0.37 ꢁ 0.06
0.16 ꢁ 0.16 ꢁ 0.14
x
x
x
x
Bruker-CCD
52.74
20817
Mar-CCD
59.16
16519
Bruker-CCD
52.74
10395
RaxisII-IP
46.50
3396
hmax (°)
Number of unique reflections
Number of observed reflections
Number of parameters
Sb
14253
778
1.012
15609
712
1.00
5888
537
2502
272
1.019
1.066
R indices [I > 2rðIÞ]a
R1 ¼ 0:0686,
wR2 ¼ 0:1715
R1 ¼ 0:1266,
wR2 ¼ 0:2102
R1 ¼ 0:0772,
wR2 ¼ 0:2095
R1 ¼ 0:787,
wR2 ¼ 0:2122
3.055, )1.047
R1 ¼ 0:0577,
wR2 ¼ 0:1366z
R1 ¼ 0:1135,
wR2 ¼ 0:1654
0.351, )0.245
R1 ¼ 0:0887,
wR2 ¼ 0:2386
R1 ¼ 0:1188,
wR2 ¼ 0:2602
0.707, )0.591
R indices (all data)a
ꢀ3
ꢀ
Maximum difference peak and hole (e A
P
)
1.070, )0.638
P
P
P
2
2
1=2
a R1 ¼ jjFoj ꢀ jFcjj= jFoj, wR2 ¼ f ½wðFo2 ꢀ Fc2Þ ꢂ= ½wðFo2Þ ꢂg (sometimes denoted as Rw2).
P
b Goodness-of-fit ¼ S ¼ f ½wðFo2 ꢀ Fc2Þ ꢂ=ðn ꢀ pÞg1=2, where n is the number of reflections, and p is the total number of refined parameters.
2
Fig. 3. ORTEP drawing of complex 4. Thermal ellipsoids are drawn to
the 50% probability level. The tetrahedral twist angle for 4 was 17.6°.
Fig. 4. ORTEP drawing of complex 6. Thermal ellipsoids are drawn to
the 50% probability level. The tetrahedral twist angle for 6 was 11.3°.

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A.S. Ionkin, W.J. Marshall / Journal of Organometallic Chemistry 689 (2004) 1057–1063
4.2. 4,400-Bis(trimethylsilyl)-[1,10;30,100]terphenyl-20-yl-
amine (10)
125.1, 129.4, 130.6, 132.8, 133.8, 139.5, 141.7, 146.3,
168.8. Anal. Calc. for C52H64N2Si4: C, 75.30; H, 7.78;
N, 3.38. Found: C, 75.04; H, 7.76; N, 3.35%. LC/MS
MW is 828. The structure was proved by X-ray analysis.
15.0 g (0.0773 mol) of 4-trimethylsilylphenylboronic
acid (8), 6.46 g (0.026 mol) of 2,6-dibromophenylamine
(7), 30.21 g (0.086 mol) of cesium carbonate, 0.37 g
(0.00040 mol) of tris(dibenzylideneacetone)dipalladium,
0.37 g (0.00116 mol) di-1-adamantylphosphine oxide
(13) and 125 ml of dioxane were refluxed for 1 h. The
reaction mixture was cooled to room temperature, fil-
tered and the solvent was removed under vacuum. The
resulting mixture was purified by chromatography on
silica gel with eluent petroleum ether/ethyl ether at 10/
0.5. Yield of 4,400-bis(trimethylsilyl)-[1,10;30,100]terphenyl-
20-ylamine (10) was 4.79 g (48%) with m.p. 92.44 °C. 1H
NMR (CDCl3) 0.10 (s, 18H, Me3Si), 3.75 (s, 2H, NH2),
6.66–7.45 (m, arom. 11H). Anal. Calc. for C24H31NSi2:
C, 73.97; H, 8.02; N, 3.59. Found: C, 74.18; H, 7.95; N,
3.50%. GC/MS MW is 389.
4.5. 2,3-Butanedione-bis(3,300-bis(trimethylsilyl)-[1,10;30,
100]terphenyl-20-ylimine) (17)
6.75
g
(0.0173 mol) of 3,300-Bis(trimethylsilyl)-
[1,10;30,100]terphenyl-20-ylamine (11), 1.38 g (0.0077 mol)
of 2,2,3,3-tetramethoxybutane (15), 50 mg of para-tolu-
enesulfonic acid and 50 ml of xylenes were refluxed under
argon for 5 h. The reaction mixture was allowed to cool
off to RT and the formed methanol and xylenes were
removed under vacuum. The product was purified by
chromatography on silica gel with eluent petroleum
ether/ethyl ether at 10/2. Yield of 2,3-butanedione-
bis(3,300-bis(trimethylsilyl)-[1,10; 30,100]terphenyl-20- yli-
mine) 17 was 0.62 g (9.66%) with m.p.219.96 °C. 1H
NMR (CDCl3) 0.10 (s, 36H, Me3Si), 1.26 (s, 6H, CH3),
6.78–7.40 (m, arom. 22H). 13C NMR (CDCl3) 0.2, 17.3,
125.0, 128.0, 130.6, 130.7, 132.6, 135.2, 140.3, 140.7,
147.1, 167.9. Anal. Calc. for C52H64N2Si4: C, 75.30;
H, 7.78; N, 3.38. Found: C, 75.10; H, 7.74; N, 3.37%. LC/
MS MW is 828. The structure was proved by X-ray
analysis.
4.3. 3,300-Bis(trimethylsilyl)-[1,10;30,100]terphenyl-20-yl-
amine (11)
15.0 g (0.0773 mol) of 3-trimethylsilylphenylboronic
acid (9), 8.24 g (0.033 mol) of 2,6-dibromophenylamine
(7), 30.21 g (0.086 mol) of cesium carbonate, 1.06 g
(0.0012 mol) of tris(dibenzylideneacetone)dipalladium,
0.65 g (0.0028 mol) di-tert-butyltrimethylsilanylmethyl-
phosphane (14) and 100 ml of dioxane were stirred at
room temperature for 12 h. The reaction mixture was
filtered and the solvent was removed under vacuum. The
resulting viscous liquid was purified by chromatography
on silica gel with eluent petroleum ether/ethyl ether at
10/0.5. Yield of 3,300-bis(trimethylsilyl)-[1,10;30,100]ter-
phenyl-20-ylamine (11) was 4.73 g (37%) with m.p. 38.47
°C. 1H NMR (CDCl3) 0.05 (s, 18H, Me3Si), 3.80 (s,
broad, 2H, NH2), 6.70–7.55 (m, arom. 11H). Anal. Calc.
for C24H31NSi2: C, 73.97; H, 8.02; N, 3.59. Found: C,
73.89; H, 7.92; N, 3.54%. GC/MS MW is 389.
4.6. Nickel(1+), [N,N0-(1,2-dimethyl-1,2-ethanediylid-
ene)bis(4,40-bis(trimethylsilyl)-[1,10;30,100]terphenyl-
20-ylamine](g3-2-propenyl)-,tetrakis[3,5-bis(trifluoro
methyl)phenyl] borate (1)) (3)
0.175 g (0.00021 mol) of 2,3-Butanedionebis(4,400-
bis(trimethylsilyl)-[1,10;30,100]terphenyl-20- ylimine) (16),
0.0285 g (0.000105 mol) of nickel allyl chloride dimer
(18), 0.187 g (0.00021 mol) of sodium tetrakis[3,5-
bis(trifluoromethyl)phenyl] borate (19) and 5 ml of ethyl
ether were stirred at RT for 12 h. The resulting reaction
mixture was filtered through Celiteâ, and the solvent was
evaporated in vacuum. The residue was washed with 10
ml of pentane and dried affording 0.31 g (82%) yield
4.4. 2,3-Butanedione-bis(4,400-bis(trimethylsilyl)-[1,10;30,
100]terphenyl-20-ylimine) (16)
1
of above nickel compound 3. H NMR (CD2Cl2) 0.19
(s, 36H, Me3Si), 1.25 (s, 6H, CH3), 1.65 (s, b, 2-allyl-H),
2.55 (s, b, 2-allyl-H), 5.14 (s, 1H central allyl-H),
6.95-7.43 (m, arom. 34 H). 13C NMR (CDCl3), (selected
signals) 180.2 (s, C@N). Anal. Calc. for C87H81BF24-
N2NiSi4: C, 58.30; H, 4.55; N, 1.56. Found: C, 58.27; H,
4.54; N, 1.41%.
3.63 g (0.0093 mol) of 4,400-Bis(trimethylsilyl)-[1,10;
30,100]terphenyl-20-ylamine (10), 0.75 g (0.0042 mol) of
2,2,3,3-tetramethoxybutane (15), 50 mg of para-tolu-
enesulfonic acid and 50 ml of toluene were refluxed
under argon for 5 h. The reaction mixture was allowed
to cool off to RT and the formed methanol and toluene
were removed under vacuum. The product was purified
by chromatography on silica gel with eluent petroleum
ether/ethyl ether at 10/2. Yield of 2,3-butanedione-
bis(4,400-bis(trimethylsilyl)-[1, 10;30,100]terphenyl-20- yli-
4.7. Nickel(1+), [N,N0-(1,2-dimethyl-1,2-ethanediylid-
ene)bis(3,30-bis(trimethylsilyl)-[1,10;30,100]terphenyl-
20-ylamine](g3-2-propenyl)-, tetrakis[3,5-bis(trifluoro-
methyl)phenyl] borate (1)) (5)
1
mine) (16) was 0.54 g (16%) with m.p. 207.05 °C. H
NMR (CDCl3) 0.12 (s, 36H, Me3Si), 1.02 (s, 6H, CH3),
6.95–7.43 (m, arom. 22H). 13C NMR (CDCl3) 0.0, 18.7,
0.20 g (0.00024 mol) of 2,3-Butanedionebis(3,300-
bis(trimethylsilyl)-[1,10;30,100]terphenyl-20- ylimine) (17),

A.S. Ionkin, W.J. Marshall / Journal of Organometallic Chemistry 689 (2004) 1057–1063
1063
0.033 g (0.00012 mol) of nickel allyl chloride dimer (18),
5. Supplementary material
0.214 g (0.00024 mol) of sodium tetrakis[3,5-bis(triflu-
oromethyl)phenyl] borate (19) and 5 ml of ethyl ether
were stirred at RT for 12 h. The resulting reaction
mixture was filtered through Celiteâ, and the solvent
was evaporated in vacuum. The residue was washed
with 10 ml of pentane and dried affording 0.31 g (82%)
CCDC contains the supplementary crystallographic
data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/conts/retrieving.html
(or from the Cambridge Crystallographic Data Centre,
12, Union Road, Cambridge CB2 1EZ, UK; fax: +44
1223 336033; or deposit@ccdc.cam.ac.uk). The deposi-
tion numbers are CCDC 210401–210404 for the com-
pounds 4, 6, 16, 17 correspondingly.
1
yield of above nickel compound 5. H NMR (CD2Cl2)
0.20 (s, 36H, Me3Si), 1.40 (s, 6H, CH3), 1.80 (s, b,
2-allyl-H), 2.65 (s, b, 2-allyl-H), 5.20 (s, 1H central allyl-
H) 6.70–7.60 (m, arom. 34H). 13C NMR (CDCl3),
(selected signals) 177.9 (s, C@N). Anal. Calc. for
C87H81BF24N2NiSi4: C, 58.30; H, 4.55; N, 1.56. Found:
C, 58.20; H, 4.49; N, 1.55%.
Acknowledgements
Portions of this work were performed at the DuPont-
Northwestern-Dow Collaborative Access Team (DND-
CAT) Synchrotron Research Center located at Sector 5
of the Advanced Photon Source at Argonne National
Laboratory. DND-CAT is supported by the E.I. Du-
Pont de Nemours & Co., The Dow Chemical Company,
the US National Science Foundation through Grant
DMR-9304725 and the State of Illinois through the
Department of Commerce and the Board of Higher
Education Grant IBHE HECA NWU 96. Use of the
Advanced Photon Source was supported by the US
Department of Energy, Basic Energy Sciences, Office of
Energy Research under Contract No. W-31-102-Eng-38.
Authors wish to thank Kurt Adams for funding X-ray
research, and Jerald Feldman for valuable suggestions
and proofreading the manuscript, and Zdzislaw Wawr-
zak for help with synchrotron experiments.
4.8. Nickel(1+), [N,N0-(1,2-dimethyl-1,2-ethanediylid-
ene)bis(4,40-bis(trimethylsilyl)-[1,10;30,100]terphenyl-20-
ylamine](g3-2-propenyl)-, hexafluoroantimonate (1)) (4)
0.19 g (0.00029 mol) of 2,3-Butanedionebis(4,400-
bis(trimethylsilyl)-[1,10;30,100]terphenyl-20- ylimine) (16),
0.031 g (0.00046 mol) of nickel allyl chloride dimer (18),
0.079 g (0.00023 mol) of silver hexafluoroantimonate
(20) and 40 ml of ethyl ether were stirred at RT for 12 h.
The resulting reaction mixture was filtered through
Celiteâ, and the solvent was evaporated in vacuum.
The residue was recrystallized from benzene affording
0.24 g (75%) yield of above nickel compound 4 with
m.p. 271.02 °C. 1H NMR (CD2Cl2) 0.21 (s, 36H,
Me3Si), 1.34 (s, 6H, CH3),1.40 (s, b, 2-allyl-H), 2.50
(s, b, 2-allyl-H), 5.20 (s, 1H central allyl-H), 7.10–7.70
(m, arom. 22H). 13C NMR (CDCl3), (selected signals)
180.5 (s, C@N). Anal. Calc. for C55H69F6N2NiSbSi4: C,
56.71; H, 5.97; N, 2.40. Found: C, 56.83; H, 6.09; N,
2.41%.
References
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