Article
Inorganic Chemistry, Vol. 48, No. 19, 2009 9499
Table 4. Crystallographic Data and Structure Refinement for Compounds 1, 3, 4, 5, and 6a
1
3
4b
5b
6b
empirical formula
formula weight
C28H33NO4Ti
495.47
orthorhombic, P212121 triclinic, P1
C38H37NO4Ti
619.61
C131H124F4N4O16Ti4 C139.40H124F8N4O16Ti4 C135H128N4O16F20Ti4
2634.08
2278.03
monoclinic, P21/n
14.0275(7)
2454.92
monoclinic, P21/n
14.0922(8)
crystal system, space group
˚
monoclinic, P21/n
14.4822(6)
25.7823(8)
16.9356(6)
a [A]
9.8007(3)
12.0225(5)
21.8908(8)
11.3277(5)
11.8376(5)
14.6005(7)
72.2383(16)
69.0925(15)
63.7256(11)
1614.48(12)
2
˚
b [A]
24.9336(11)
17.3094(7)
25.1053(13)
17.4834(11)
˚
c [A]
R [deg]
β [deg]
γ [deg]
93.3960(14)
93.0577(18)
94.8210(13)
3
˚
V [A ]
Z
Dcalcd
2579.39(16)
4
1.276
3.648
1048.00
50.6
6043.4(5)
2
1.252
6176.6(6)
2
1.320
6301.1(4)
2
1.388
1.274
3.06
μ(Mo KR) cm-1
F (000)
3.253
2380.00
48.8
3.281
2552.80
48.2
3.396
2724.00
50.7
652.00
50.7
2θmax [deg]
no. of reflections collected/unique 21447/2668
(Rint= 0.044)
2333
13537/5898
(Rint = 0.031)
4655
1.005
0.0425, 0.0803
0.40/-0.32
45019/9897
(Rint = 0.077)
5028
1.085
0.0616, 0.0709
0.88/-0.45
44799/9796
(Rint = 0.136)
3460
1.002
0.0642, 0.1612
0.41/-0.33
51321/11493
(Rint = 0.071)
6559
1.002
0.0497, 0.1334
0.63/-0.37
observed reflections [I > 2σ(I)]
gof
1.003
0.0338, 0.0912
0.28/-0.30
R1, wR2 [I > 2σ(I)]
largest diff peak/hole [e A
-3
˚
]
a Detailed results are shown in the Supporting Information. b The crystal contained toluene in the formula (with certain ratio).
aryl-Me). 13C{1H} NMR (CDCl3): δ 163.8, 159.1, 131.1, 129.5,
127.7, 127.6, 127.4, 124.8, 122.9, 120.4 (aryl), 72.0 (CH2O), 57.2
(NCH2-aryl), 56.8 (NCH2CH2), 20.5 (aryl-Me), 17.5 (terminal
aryloxo-Me), 16.2 (aryl-Me). Anal. Calcd for C28H33NO4Ti: C,
67.88; H, 6.71; N, 2.83. Found: C, 67.78; H, 6.90; N, 2.75.
Synthesis of Ti(O-2,6-Ph2C6H3){(O-2,4-Me2C6H2-6-CH2)2-
(OCH2CH2)N} (3). The procedure for synthesis of 3 was con-
ducted by the similar procedure for 1, except that 2,6-
Ph2C6H3OH was used in place of 2,6-Me2C6H3OH. Yield
81%. 1H NMR (C6D6): δ 7.92 (dd, 4H, J=7.7 Hz, phenyl-H),
7.36 (d, J=7.7 Hz, 2H, phenyl-H), 7.20 (t or dd, 4H, J=7.7 Hz,
phenyl-H), 7.04 (t, 2H, J=7.3 Hz, phenyl-H), 6.93 (t, 1H, J=
7.3 Hz, phenyl-H), 6.76 (br.s, 2H aryl-H), 6.44 (br.s, 2H aryl-H),
3.59 (t, 2H, CH2O), 3.06 and 2.97 (d, 4H, NCH2-aryl), 2.14 (s,
8H, aryl-Me; NCH2CH2 peak merges with the aryl-Me peak),
1.95 (s, 6H, aryl-Me). 13C{1H} NMR (C6D6): δ 161.3, 159.4,
141.1, 133.4, 131.3, 130.8 130.4, 129.1, 127.8, 127.6, 126.4, 125.1,
123.1, 121.2 (aryl), 72.3 (CH2O), 57.2 (NCH2-aryl), 56.9
(NCH2CH2), 20.7 (aryl-Me), 16.1 (aryl-Me). Anal. Calcd for
C38H37NO4Ti: C, 73.66; H, 6.02; N, 2.26. Found: C, 73.06; H,
6.07; N, 2.06.
conducted by the similar procedure for 1, except that C6H5OH
was used in place of 2,6-Me2C6H3OH. Yield 86%. H NMR
1
(CDCl3): δ 6.83 (br.s, 2H, aryl-H), 6.70 (br.s, 2H, aryl-H), 4.54
(t, 2H, CH2O), 3.99 and 3.83 (br, 4H, NCH2-aryl), 3.34 (s, 2H,
NCH2CH2), 2.20 (s, 6H, aryl-Me), 2.00 (s, 6H, aryl-Me). 19F
NMR (CDCl3): δ -10.48 (b, d, orthoF), -17.59 (b, t, paraF),
-22.85 (b, t, metaF). Anal. Calcd for C52H48F10N2O8Ti2 9/5:
3
C, 60.59; H, 4.91; N, 2.19. Found: C, 60.70; H, 4.94; N, 2.41.
Crystallographic Analysis. All measurements were made on
a Rigaku RAXIS-RAPID imaging plate diffractometer with
graphite-monochromated Mo KR radiation. All structures
were solved by direct methods and expanded using Fourier
techniques,21 and the non-hydrogen atoms were refined
anisotropically. Hydrogen atoms were included but not
refined. All calculations for complexes 1, 3-6 were per-
formed using the crystal structure crystallographic software
package.22 Selected crystal collection parameters are sum-
marized in Table 4, and the detailed structure reports
including their CIF files were shown in the Supporting
Information.
Polymerization of Ethylene. Ethylene polymerizations were
conducted in toluene or in n-octane by using a 100 mL scale
autoclave. The typical procedure (run 1, Table 3) was performed
as follows. Solvent (29.0 mL) and d-MAO (3.0 mmol) prepared
by removing toluene and AlMe3 from the commercially avail-
able MAO (PMAO-S, Tosoh Finechem Co.) were charged into
an autoclave in the drybox, and the apparatus was placed under
an ethylene atmosphere (1 atm). After the addition of toluene or
n-octane solution (1.0 mL) containing catalyst via a syringe, the
reaction apparatus was pressurized to 7 atm (total 8 atm), and
the mixture was stirred magnetically for 10 or 60 min. After the
above procedure, ethylene was purged, and the mixture was then
poured into MeOH (150 mL) containing HCl (10 mL). The
resultant polymer was collected on a filter paper by filtration
and was adequately washed with MeOH and then dried under
vacuum.
Synthesis of [Ti(O-2-FC6H4){(O-2,4-Me2C6H2-6-CH2)2(μ2-
OCH2CH2)N}]2 (4). The procedure for synthesis of 4 was
conducted by the similar procedure for 1, except that
2-FC6H4OH was used in place of 2,6-Me2C6H3OH. Yield 69%.
1H NMR (CDCl3): δ 6.64-6.98 (m, 4H, terminal aryl-H), 6.88
(br.s, 2H, aryl-H), 6.70 (br.s, 2H, aryl-H), 4.47 (br.s, 2H, CH2O),
4.00 and 3.76 (br, 4H, NCH2-aryl), 3.30 (s, 2H, NCH2CH2), 2.21
(s, 6H, aryl-Me), 2.00 (s, 6H, aryl-Me). 19F NMR (CDCl3)
δ 16.75 (s). Anal. Calcd for C52H56F2N2O8Ti2 4/3 toluene:
3
C, 67.35; H, 6.14; N, 2.56. Found: C, 67.02; H, 6.25; N, 2.72.
Synthesis of [Ti(O-2,6-F2C6H3){(O-2,4-Me2C6H2-6-CH2)2-
(μ2-OCH2CH2)N}]2 (5). The procedure for synthesis of 5 was
conducted by the similar procedure for 1, except that 2,6-
F2C6H3OH was used in place of 2,6-Me2C6H3OH. Yield 82%.
1H NMR (CDCl3): δ. 6.81 (br.s, 2H, aryl-H), 6.70 (br.s, 2H,
aryl-H), 6.64 (m, 2H, terminal aryl-H), 6.51 (m, 1H, terminal
aryl-H), 4.55 (br.s, 2H, CH2O), 3.99 and 3.83 (br, 4H, NCH2-
aryl), 3.30 (s, 2H, NCH2CH2), 2.21 (s, 6H, aryl-Me), 2.02 (s, 6H,
aryl-Me). 19F NMR (CDCl3) δ -80.48 (b, s). Anal. Calcd for
(21) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
de Delder, R.; Israel, R.; Smits, J. M. M. DIRDIF94, The DIRDIF94
program system, technical report of the crystallography laboratory; University
of Nijmegen: The Netherlands, 1994.
(22) (a) Crystal Structure 3.6.0: Crystal Structure Analysis Package;
Rigaku and Rigaku/MSC: The Woodlands, TX, 2000-2004. (b) Watkin, D. J.;
Prout, C. K.; Carruthers, J. R.; Betteridge, P. W. CRYSTALS Issue 10; Chemical
Crystallography Laboratory: Oxford, U.K., 1996.
C52H54F4N2O8Ti2 8/5 toluene: C, 65.77; H, 5.83; N, 2.43.
3
Found: C, 65.75; H, 5.88; N, 2.35.
Synthesis of [Ti(OC6F5){(O-2,4-Me2C6H2-6-CH2)2(μ2-
OCH2CH2)N}]2 (6). The procedure for synthesis of 6 was