BunLi (0.60 cm3 of 2.45 M solution in hexanes, 1.5 mmol). The
mixture was stirred at −78 °C for 1 h, allowed to reach room tem-
perature and stirred for 17 h. This produced a yellow suspension
that was isolated by filtration to yield an air sensitive yellow solid.
Yield: 0.258 g, 64%. H (C6D6) 0.7–1.7 (10H, m, cyclohexyl CH2s),
2.11 (6H, s, mesityl methyls), 2.25 (3H, s, mesityl methyl), 2.67
(1H, br t, cyclohexyl CH to imino N), 6.35–6.55 (2H, m, aromat-
ics), 6.81 (2H, s, mesityl aromatics), 7.02 (1H, t, aromatic), 7.22
(1H, d, aromatic), 8.06 (1H, s, C(H)N).
methyl), 2.97 (3H, s, methyl), 5.08 (1H, br t, cyclohexyl CH to
imino N), 6.41 (1H, d, aromatic), 6.97–7.05 (3H, m, aromatic),
8.03 (1H, d, aromatic). 13C{1H} C (d8-thf) 21.24 (mesityl methyls),
22.26, 26.56 (methyls), 27.79, 28.70, 28.89, 32.18, 36.40 (cyclo-
hexyl CH2s) 66.17 (cyclohexyl CH to imino N), 119.90, 121.35
(aromatic CHs), 130.50 (quaternary aromatic), 131.53, 132.85,
134.39 (aromatic CHs), 137.70, 137.86, 139.00, 151.54 (quaternary
aromatics), 177.48 (CN).
[2-(1-cyclohexylimino-ethyl)-N-(2,4,6-trimethylphenyl)-
anilido]-zirconium-(tetrachloride) diethylammonium salt, 4
[2-(1-cyclohexylimino-ethyl)-N-(2,4,6-trimethylphenyl)-
anilido]-zirconium-bis-(diethylamido)-(chloride), 1, and
[2-(1-cyclohexylamido-vinyl)-N-(2,4,6-trimethylphenyl)-
anilido]-zirconium-(diethylamido)-(chloride)-
tetrahydrofuran, 2
Complex 3 (100 mg) was dissolved in thf (10 cm3) and layered with
petroleum (10 cm3) in a Schlenk tube. The tube was left to stand for
ca. one week and afforded a small crop of yellow crystals of 4.
[2-(1-cyclohexylamido-1-dimethylamino-ethyl)-N-(3,5-
dimethylphenyl)-anilido]-titanium-(dimethylamido)-(chloride),
5a, and [2-(1-cyclohexylamido-1-dimethylamino-ethyl)-N-(3,5-
dimethylphenyl)-anilido]-titanium-(dichloride), 5b
To a stirred and cooled (−78 °C) solution of Zr(NEt2)2Cl2(thf)2
(1.35 g, 3.0 mmol) in thf (50 cm3) was added slowly via cannula
a cooled (−78 °C) solution of LmesLi (1.02 g, 3.0 mmol) in thf
(50 cm3). The reaction was stirred at −78 °C for 1 h, allowed to
reach room temperature and then stirred for 18 h. From the bright
orange solution the volatiles were removed in vacuo, the residue
extracted into petroleum (ca. 100 cm3) and filtered through Celite.
The bright orange filtrate was concentrated to ca. 15 cm3 and cooled
to −30 °C overnight to produce yellow, X-ray diffraction quality
crystals of 1. Yield: 0.90 g, 50%. (Found: C, 61.3; H, 8.3; N, 9.3.
C31H49ClN4Zr requires C, 61.6; H, 8.2; N, 9.3%). H (C6D6): 0.84
(12H, t, NCH2CH3), 1.10–2.80 (10H, m, cyclohexyl CH2s), 2.02
(3H, s, imino methyl), 2.15 (6H, s, mesityl methyls), 2.24 (3H,
s, mesityl methyl), 3.16–3.38 (8H, m, NCH2CH3), 3.74 (1H, br t,
cyclohexyl CH to imino N), 6.53 (1H, dt, aromatic), 6.62 (1H, d,
aromatic), 6.86–6.95 (3H, m, mesityl aromatics and one aromatic),
7.24 (1H, dd, aromatic).
To a stirred, cooled (−78 °C) solution of Ti(NMe2)2Cl2 (0.104 g,
0.5 mmol) in thf (15 cm3) was added slowly a solution of LxylLi
(0.163 g, 0.5 mmol) in thf (15 cm3). The dark red solution was al-
lowed to reach room temperature over ca. 10 h and stirred for a fur-
ther 2 h. Removal of the volatiles in vacuo, extraction of the residue
into petroleum (2 × 30 cm3), filtration through Celite, concentration
of the bright red solution to ca. 20 cm3 and cooling at −30 °C for
48 h gave an orange/red powder.
Major product 5a. H (C6D6) 0.80–1.80 (10H, m, cyclohexyl
CH2s), 1.40 (3H, s, methyl to cyclohexylamido and amino
groups), 1.94 (3H, s, amino methyl), 2.18 (6H, s, xylyl methyls),
2.51 (3H, s, amino methyl), 3.17 (6H, s, dimethylamido N(CH3)2),
3.30–3.50 (1H, m, cyclohexyl CH to cyclohexylamido N), 6.73
(1H, s, xylyl aromatic), 6.77–6.86 (2H, m, aromatics), 7.01 (1H,
dt, aromatic), 7.13 (1H, dd, aromatic), 7.24 (2H, xylyl aromatics).
(Found: C, 64.5; H, 7.8; N, 8.5. C26H39ClN3TiCl requires C, 65.5;
H, 8.2; N, 8.8%).
13C{1H} C (C6D6): 13.25 (NCH2CH3), 20.25 (mesityl methyls),
21.62 (mesityl methyl), 23.75 (imino methyl), 26.24, 27.02, 32.35
(cyclohexyl CH2s), 41.48 (NCH2CH3), 65.85 (cyclohexyl CH to
imino N), 117.42, 120.50 (aromatic CHs), 122.86, 129.07 (quater-
nary aromatics), 130.32, 131.77, 133.25 (aromatic CHs), 134.19,
135.61, 150.71 (quaternary aromatics), 169.75 (CN).
By concentration of the supernatant solution 2 was isolated as
yellow orange air sensitive powder in variable quantities depending
on the scale of the reaction.
Minor product 5b. H (C6D6) 0.70–2.70 (10H, m, cyclohexyl
CH2s), 1.26 (3H, s, methyl to cyclohexylamido and amino
groups), 1.92 (3H, amino methyl), 2.13 (6H, s, xylyl methyls),
2.25 (3H, s, amino methyl), 2.40–2.60 (1H, m, cyclohexyl CH
to cyclohexylamido N), 6.35 (1H, dd, aromatic), 6.70 (2H, s, xylyl
aromatics), 6.79 (1H, dt, aromatic), 6.87 (1H, dt, aromatic), 6.99
(1H, dd, aromatic), 7.15 (1H, s, xylyl aromatic).
13C{1H}: C (C6D6) 16.26 (methyl to cyclohexylamido and
amino groups), 21.90 (xylyl methyls), 26.30, 27.05, 27.30, 35.07,
37.19 (cyclohexyl CH2s), 40.52, 43.24 (amino methyls), 67.30
(cyclohexyl CH to cyclohexylamido N), 86.12 (carbon to cy-
clohexylamido and amino groups), 112.47, 123.64, 128.03, 129.00
(aromatic CHs), 129.68 (quaternary aromatic), 129.84, 130.46 (aro-
matic CHs), 140.75, 144.90, 151.56 (quaternary aromatics). (Found:
C, 61.0; H, 6.8; N, 5.6. C24H33Cl2N2Ti requires C, 61.6; H, 7.1; N,
6.0%). X-ray quality crystals were grown from diethyl ether.
H (C6D6) 0.75–1.80 (10H, cyclohexyl CH2s), 0.90 (6H, t,
NCH2CH3)2), 1.26 (4H, br t, thf), 2.19 (3H, s, mesityl methyl), 2.27
(3H, s, mesityl methyl), 2.56 (3H, s, mesityl methyl), 2.85–3.0
(2H, m, N(CH2CH3)2), 3.10–3.25 (1H, m, cyclohexyl CH to ene-
amido N), 3.35–3.55 (2H, m, N(CH2CH3)2), 3.78 (4H, br t, thf),
4.52 (1H, s, CCH2), 4.96 (1H, s, CCH2), 6.11 (1H, d, aromatic),
6.76 (1H, t, aromatic), 6.90–7.05 (3H, m, aromatics), 7.41 (1H, d,
aromatic).
13C{1H} C (C6D6) 13.14 (NCH2CH3)2), 19.37, 19.74, 21.80
(mesityl methyls), 25.98 (thf), 26.24, 26.97, 35.18, 36.91, 37.12
(cyclohexyl CH2s), 41.26 (NCH2CH3)2), 61.06 (cyclohexyl CH
to ene-amido N), 71.75 (thf), 102.77 (CCH2), 112.87 (aromatic
CH), 113.48 (quaternary aromatic), 117.51, 128.08 (aromatic
CHs), 129.80 (quaternary aromatic), 130.25, 131.12, 131.25
(aromatic CHs), 135.14, 142.61, 152.84, 155.92 (quaternary aro-
matics), 171.71 [ArC(N)CH2]. (Found: C, 61.5; H, 7.2; N, 6.5.
C31H46ClON3Zr requires C, 61.7; H, 7.7; N, 6.7%).
[2-(1-cyclohexylamido-1-dimethylamino-
ethyl)-N-(2,4,6-trimethylphenyl)-anilido]-
titanium-(dimethylamide)-(chloride), 6a, and
[2-(1-cyclohexylamido-1-dimethylamino-ethyl)-N-(2,4,6-
trimethylphenyl)-anilido]-titanium-(dichloride), 6b
[2-(1-cyclohexylimino-ethyl)-N-(2,4,6-trimethylphenyl)-
anilido]-zirconium-(trichloride), 3
These were prepared following a method similar to the above from
Ti(NMe2)2Cl2 (0.104 g, 0.5 mmol) and LmesLi (0.170 g, 0.5 mmol)
in thf (15 cm3).
To a stirred solution of 1 (0.80 g, 1.33 mmol) in benzene (20 cm3)
was added trimethylchlorosilane (0.7 cm3, 5.5 mmol). Upon addi-
tion the benzene solution became bright orange and after stirring
for 30 min a bright yellow precipitate was produced. Stirring was
continued for a total of 3 h when the product was collected by filtra-
tion, washed with petrol (ca. 50 cm3) and dried in vacuo to yield
a yellow solid. Yield: 0.590 g, 84%. H (d8-thf) 1.30–2.20 (10H,
m, cyclohexyl CH2s), 2.26 (3H, s, mesityl methyls), 2.39 (3H, s,
Major product 6a. H (C6D6) 0.80–1.65 (10H, m, cyclohexyl
CH2s), 1.47 (3H, s, methyl to cyclohexylamido and amino
groups), 1.96 (3H, s, amino methyl), 2.12 (3H, s, mesityl methyl),
2.22 (3H, s, mesityl methyl), 2.46 (3H, s, mesityl methyl), 2.49
(3H, s, amino methyl), 3.13 (6H, s, dimethylamido N(CH3)2),
D a l t o n T r a n s . , 2 0 0 4 , 2 5 5 6 – 2 5 6 2
2 5 6 1