[ONXO]-Type Amine Bis(phenolate) Zr and Hf Complexes
Organometallics, Vol. 21, No. 4, 2002 669
Ta ble 8. Cr ysta l Da ta a n d Str u ctu r e Refin em en t P a r a m eter s for 2a , 3a , 1b, a n d 3b
2a
3a
1b
2b
3b
formula
fw
temp (K)
cryst syst
space group
a (Å)
C
47H65NO3Zr
C47H65NO2SZr‚C4H10
873.40
110
orthorhombic
Pbca
18.2920(4)
18.6030(5)
28.5410(8)
O
C48H68N2O2Hf‚C5H12
955.68
110
orthorhombic
Pbca
18.4040(2)
19.1730(2)
28.2250(4)
C47H65NO3Hf‚C5H12
942.64
110
orthorhombic
Pbca
18.1570(3)
18.6620(3)
28.4990(5)
C47H65NO2SHf‚C4H10
960.67
110
orthorhombic
Pbca
18.2820(3)
18.6190(3)
28.5240(5)
O
783.22
110
monoclinic
P21/c
10.4860(6)
25.343(2)
17.348(1)
107.168(5)
4404.8(5), 4
1.181
0.71070
0.288
7876
4302
0.066
b (Å)
c (Å)
â (deg)
V (Å3), Z
Fcalcd (g cm-3
λ (Å)
9712.1(4), 8
1.195
0.71070
0.309
7405
4356
0.062
0.105
0.141
9959.5(2), 8
1.275
0.71070
2.134
9063
6828
0.041
0.095
0.064
9656.8(3), 8
1.297
0.71070
2.201
10 989
5760
0.043
9709.4(3), 8
1.314
0.71070
2.231
8864
5759
0.036
0.075
0.073
)
µ (mm-1
)
no. of rflns measd
no. of indep rflns
R1 (I > 2σ(I))
wR2 (I > 2σ(I))
R1 (all data)
0.142
0.147
0.097
0.114
wR2 (all data)
0.174
0.979
0.133
1.043
0.106
0.980
0.125
0.902
0.087
1.018
GOF (F2)
Com p ou n d 2. A solution of 2,4-di-tert-butylphenol (5.0 g,
24.2 mmol), 2-methoxyethylamine (1.05 mL, 12.1 mmol), and
36% aqueous formaldehyde (3.0 mL, 36.0 mmol) in methanol
(10 mL) was stirred and refluxed for 7 days. The mixture was
cooled and the supernatant liquid decanted. The remaining
oil was crystallized from methanol (25 mL), affording colorless
crystals of the product (2.6 g, 42% yield). Mp: 135 °C. HRMS:
72.25; H, 8.01; N, 2.13. 1H NMR (C6D6): δ 7.74 (d, J ) 7.4 Hz,
2H), 7.60 (d, J ) 2.4 Hz, 2H), 7.35 (t, J ) 7.7 Hz, 2H), 7.03 (t,
J ) 7.3 Hz, 1H), 6.90 (m, 4H), 6.76 (t, J ) 7.6 Hz, 2H), 6.56 (t,
J ) 7.3 Hz, 1H), 3.51 (d, J ) 13.4 Hz, 2H, ArCH2), 2.85 (s, 2H,
PhCH2), 2.60 (d, J ) 13.5 Hz, 2H, ArCH2), 2.49 (s, 2H, PhCH2),
2.48 (s, 3H, OCH3), 2.21 (t, J ) 5.3 Hz, 2H, CH2), 1.90 (t, J )
5.3 Hz, 2H, CH2), 1.85 (s, 18H, C(CH3)3), 1.36 (s, 18H, C(CH3)3).
13C NMR (C6D6): δ 159.0, 146.7, 141.8, 137.2, 129.9, 128.2,
125.9, 125.6, 125.3, 123.5, 121.3, 73.9 (CH2), 68.4 (PhCH2), 67.0
(PhCH2), 65.2 (ArCH2), 61.8 (OCH3), 51.7 (CH2), 36.2 (C(CH3)3),
35.1 (C(CH3)3), 32.6 (C(CH3)3), 31.0 (C(CH3)3).
2a /B(C6F 5)3. One equivalent of B(C6F5)3 was added to 2a
in d5-chlorobenzene. 1H NMR (C6D5Cl): δ 7.68 (d, J ) 2.0 Hz,
2H), 7.63 (d, J ) 7.2 Hz, 2H), 7.36-7.16 (m, 4H), 7.08 (t, J )
7.6 Hz, 4H), 6.93 (t, J ) 7.0 Hz, 2H), 3.80 (d, J ) 13.9 Hz, 2H,
ArCH2), 3.50 (br s, 2H, PhCH2B), 3.38 (d, J ) 13.9 Hz, 2H,
ArCH2), 3.31 (s, 3H, OCH3), 3.17 (m, 2H, CH2), 3.12 (s, 2H,
PhCH2Zr), 2.59 (m, 2H, CH2), 1.67 (s, 18H, C(CH3)3), 1.47 (s,
18H, C(CH3)3). 19F NMR (C6D5Cl): δ -130.72 (o), -164.21 (p),
-166.95 (m).
m/z calcd 511.4026, found 511.4032. Anal. Calcd for C33H53
-
NO3: C, 77.45; H, 10.44; N, 2.74. Found: C, 77.70; H, 10.72;
1
N, 2.79. H NMR (CDCl3): δ 7.21 (d, J ) 2.0 Hz, 2H), 6.90 (d,
J ) 2.0 Hz, 2H), 3.75 (s, 4H, CH2) 3.57 (t, J ) 5.0 Hz, 2H,
CH2), 3.48 (s, 3H, OCH3), 2.76 (t, J ) 5.0 Hz, 2H, CH2) 1.40
(s, 18H, C(CH3)3), 1.28 (s, 18H, C(CH3)3). 13C NMR (CDCl3): δ
152.8, 140.7, 136.0, 124.9, 123.4, 121.6, 71.4 (ArCH2), 58.9
(OCH3), 58.0 (CH2), 51.3 (CH2), 35.0 (C(CH3)3), 34.1 (C(CH3)3),
31.6 (C(CH3)3), 30.1 (C(CH3)3).
Com p ou n d 3. A solution of 2,4-di-tert-butylphenol (4.2 g,
20.3 mmol), 2-(methylthio)ethylamine (1 mL, 10.7 mmol), and
36% aqueous formaldehyde (3.0 mL, 36.0 mmol) in methanol
(10 mL) was stirred and refluxed for 48 h. The mixture was
cooled and the supernatant liquid decanted. The remaining
oil was crystallized from methanol, giving colorless crystals
of the product (1.5 g, 28% yield). Mp: 124 °C. HRMS: m/z calcd
527.3797. found 527.3805. Anal. Calcd for C33H53NO2S: C,
75.09; H, 10.12; N, 2.65; S, 6.07. Found: C, 74.90; H, 10.33;
N, 2.81; S, 6.01. 1H NMR (CDCl3): δ 7.23 (s, 2H), 6.90 (s, 2H),
3.65 (s, 4H, CH2), 2.74 (s, 4H, CH2), 1.99 (s, 3H, SCH3), 1.40
(s, 18H, C(CH3)3), 1.27 (s, 18H, C(CH3)3). 13C NMR (CDCl3): δ
152.4, 141.3, 136.1, 125.2, 123.7, 121.2, 57.3 (ArCH2), 51.0
(CH2), 31.5 (CH2), 34.9 (C(CH3)3), 34.1 (C(CH3)3), 31.6 (C(CH3)3),
29.6 (C(CH3)3), 14.78 (SCH3).
Com p lex 3a . Crystal data are presented in Table 8. 1H
NMR (C6D6): δ 7.72 (d, J ) 7.3 Hz, 2H), 7.57 (d, J ) 2.4 Hz,
2H), 7.34 (t, J ) 7.7 Hz, 2H), 7.04 (t, J ) 7.3 Hz, 1H), 6.90 (m,
4H), 6.78 (t, J ) 7.5 Hz, 2H), 6.58 (t, J ) 7.2 Hz, 1H), 3.58 (d,
J ) 13.4 Hz, 2H, ArCH2), 3.08 (s, 2H, PhCH2), 2.60 (d, J )
13.5 Hz, 2H, ArCH2), 2.47 (s, 2H, PhCH2), 2.07 (m, 2H, CH2),
1.82 (s, 18H, C(CH3)3), 1.35 (s, 18H, C(CH3)3), 1.37-1.26 (m,
2H, CH2), 1.00 (s, 3H, SCH3). 13C NMR (C6D6): δ 158.9, 149.8,
146.3, 142.1, 137.5, 130.0, 129.5, 128.2, 126.5, 125.5, 125.3,
123.8, 121.4, 67.0 (PhCH2), 65.7 (ArCH2), 64.4 (PhCH2), 54.7
(CH2), 36.3 (C(CH3)3), 35.1 (C(CH3)3), 34.0 (CH2), 32.6 (C(CH3)3),
31.2 (C(CH3)3), 15.3 (SCH3).
LigHfBn 2 Gen er a l P r oced u r e. A solution of 1, 2, or 3
(0.40 mmol) in toluene (2 mL) was added dropwise to a solution
of tetrabenzylhafnium (0.40 mmol) in toluene (2 mL) and
stirred at room temperature for 2 h. The toluene was removed
under vacuum, and the dibenzyl complexes 1b-3b were
obtained quantitatively as colorless solids.
Com p lex 1b. Crystal data are presented in Table 8. Anal.
Calcd for C48H68N2O2Hf: C, 65.25; H, 7.76; N, 3.17. Found:
C, 65.19; H, 7.64; N, 3.35. 1H NMR (C6D6): δ 7.65 (m, 4H),
7.39 (d, J ) 7.6 Hz, 2H), 6.99 (t, J ) 7.4 Hz, 1H), 6.92 (m,
4H), 6.76 (t, J ) 7.7 Hz, 2H), 6.55 (t, J ) 7.3 Hz, 1H), 3.49 (d,
J ) 13.5 Hz, 2H, ArCH2), 2.59 (d, J ) 13.5 Hz, 2H, ArCH2),
2.47 (s, 2H, PhCH2), 2.42 (s, 2H, PhCH2), 1.84 (s, 18H,
C(CH3)3), 1.52 (s, 6H, N(CH3)2), 1.52-1.30 (m, 4H, CH2), 1.36
(s, 18H, C(CH3)3). 13C NMR (C6D6): δ 158.0, 141.0, 137.1, 128.6,
127.2, 125.3, 124.9, 124.6, 121.9, 120.6, 79.3 (PhCH2), 72.9
(PhCH2), 64.9 (ArCH2), 60.3 (CH2), 51.3 (N(CH3)2), 35.6
(C(CH3)3), 34.4 (C(CH3)3), 31.8 (C(CH3)3), 30.7 (C(CH3)3).
LigZr Bn 2 Gen er a l P r oced u r e. A solution of 2 or 3 (0.40
mmol) in toluene (2 mL) was added dropwise to a solution of
tetrabenzylzirconium (0.40 mmol) in toluene (2 mL) at room
temperature under
a nitrogen atmosphere. The reaction
mixture was then heated to 65 °C and stirred for 2 h. The
toluene was removed under vacuum, and the dibenzyl com-
plexes 2a and 3a were obtained quantitatively as yellow solids.
Com p lex 1a .7 Anal. Calcd for C48H68N2O2Zr: C, 72.40; H,
8.61; N, 3.52. Found: C, 72.29; H, 8.49; N, 3.70.
1a /B(C6F 5)3. One equivalent of B(C6F5)3 was added to 1a
in d5-chlorobenzene. 1H NMR (C6D5Cl): δ 7.63 (m, 4H), 7.29-
7.01 (m, 8H), 6.89 (t, J ) 6.2 Hz, 2H), 3.85 (d, J ) 13.8 Hz,
2H, ArCH2), 3.47 (br s, 2H, PhCH2B), 3.27 (d, J ) 13.8 Hz,
2H, ArCH2), 3.03 (s, 2H, PhCH2Zr), 2.62 (br, 2H, CH2), 1.98
(s, 6H, N(CH3)2), 1.64 (s, 18H, C(CH3)3), 1.44 (s, 18H, C(CH3)3),
1.63-1.44 (m, 2H, CH2). 19F NMR (C6D5Cl): δ -130.64 (o),
-164.36 (p), -167.02 (m).
Com p lex 2a . Crystal data are presented in Table 8. Anal.
Calcd for C47H65NO3Zr: C, 72.07; H, 8.36; N, 1.79. Found: C,