6168 Organometallics, Vol. 23, No. 26, 2004
Basuli et al.
Synthesis of (Nacnac)ZrCl3 (1). In a reaction vessel
equipped with a stir bar was placed ZrCl4 (3.67 g, 0.016 mol)
in toluene (∼200 mL), and the suspension was cooled to -35
°C. To the cold solution was slowly added solid Li(Nacnac) (8.00
g, 0.016 mol) in portions. After it was warmed to room
temperature, the reaction mixture was heated at 80 °C for 3
days. The dark solution was then filtered to remove a dark
solid, and the filtrate was dried under reduced pressure. The
solid was dissolved in dichloromethane, filtered, and this
solution was then layered with pentane and stored at -35 °C
for 24 h to afford large yellow blocks of (Nacnac)ZrCl3 (1; 8.40
g, 0.012 mol, 75% yield, two crops).
(ZrCH2CMe3, JC-H ) 107 Hz), 43.40 (br, C(CMe3)CHC(CMe3)),
37.34 (ZrCH2CMe3), 36.22 (ZrCH2CMe3), 34.87 (C(CMe3)CHC-
(CMe3)), 34.67 (C(CMe3)CHC(CMe3)), 34.46 (CHMe2), 30.44
(CHMe2), 27.05 (CH3), 26.64 (CH3). Anal. Calcd for C45H75N2-
ClZr: C, 70.12; H, 9.80; N, 3.36. Found: C, 69.86; H, 9.48; N,
3.71.
Synthesis of (Nacnac)Zr(CH2SiMe3)2Cl (4). In a vial was
suspended (Nacnac)ZrCl3 (1; 300.3 mg, 0.43 mmol) in 20 mL
of Et2O, and the solution was cooled to -35 °C. To the cold
suspension was added dropwise a cold Et2O solution (∼10 mL)
containing LiCH2SiMe3 (84.7 mg, 0.90 mmol). After it was
warmed to room temperature, the mixture was stirred for 30
min. The solution was then filtered, and the filtrate was
concentrated and stored at -35 °C for 24 h to afford yellow
crystals of (Nacnac)Zr(CH2SiMe3)2Cl (4; 315.2 mg, 0.39 mmol,
91% yield, two crops).
Data for 1 are as follows. 1H NMR (23 °C, 399.8 MHz,
C6D6): δ 7.07 (d, C6H3, 2H), 6.96 (t, C6H3, 2H), 6.88 (d, C6H3,
2H), 6.52 (s, C(tBu)CHC(tBu), 1H), 3.87 (septet, CH(Me)2, 2H),
2.56 (septet, CH(Me)2, 2H), 1.56 (d, CHMe2, 6H), 1.36 (d,
CHMe2, 6H), 1.16 (s, C(tBu)CHC(tBu), 18H), 0.99 (d, CHMe2,
6H), 0.76 (d, CHMe2, 6H). 13C NMR (25 °C, 100.6 MHz, C6D6):
δ 167.3 (C(tBu)CHC(tBu)), 144.3 (C6H3), 141.8 (C6H3), 137.8
(C6H3), 126.5 (C6H3), 125.9 (C6H3), 124.7 (C3H3), 104.1 (C(tBu)-
CHC(tBu), JC-H ) 158 Hz), 43.17 (C(CMe3)CHC(CMe3)), 32.32
(C(CMe3)CHC(CMe3)), 29.69 (CHMe2), 27.52 (CHMe2), 26.37
(CH3), 26.25 (CH3), 25.69 (CH3), 25.57 (CH3). Anal. Calcd for
C35H53N2Cl3Zr: C, 60.10; H, 7.64; N, 4.00. Found: C, 60.09;
H, 7.60; N, 3.92.
Data for 4 are as follows. 1H NMR (23 °C, 399.8 MHz,
C6D6): δ 7.08-6.94 (m, C6H3, 6H), 6.52 (s, C(tBu)CHC(tBu),
1H), 3.87 (br, CH(Me)2, 2H), 2.46 (br, CH(Me)2, 2H), 1.53 (d,
CHMe2, 6H), 1.37 (br, CHMe2, 6H), 1.46-1.07 (overlapping
peaks, C(tBu)CHC(tBu) and CHMe2, 30H), 0.71 (s, ZrCH2-
SiMe3, 2H), 0.43 (s, ZrCH2SiMe3, 9H), 0.40 (s, ZrCH2SiMe3,
9H); the additional ZrCH2SiMe3 resonance could not be located.
13C NMR (25 °C, 100.6 MHz, C6D6): δ 138.4 (br), 125.0 (br),
96.04 (C(tBu)CHC(tBu)), 63.85 (ZrCH2SiMe3), 63.53 (ZrCH2-
SiMe3), 43.05 (br, C(CMe3)CHC(CMe3)), 30.34 (C(CMe3)CHC-
(CMe3)), 27.17 (br), 27.34 (br), 26.12 (br), 3.36 (ZrCH2SiMe3).
1H NMR (-40 °C, 399.8 MHz, C6D5CD3): δ 7.12-6.72 (m,
C6H3, 6H), 6.30 (s, C(tBu)CHC(tBu), 1H), 3.87 (br, CH(Me)2,
1H), 3.35 (br, CH(Me)2, 2H), 2.10 (br, CH(Me)2, 1H), 1.53 (br,
CHMe2, 6H), 1.33-0.92 (m, C(tBu)CHC(tBu) and CHMe2,
30H), 0.78 (s, ZrCH2SiMe3, 2H), 0.49 (s, ZrCH2SiMe3, 2H), 0.47
(s, ZrCH2SiMe3, 9H), 0.42 (s, ZrCH2SiMe3, 9H), 0.38 (d, CHMe2,
6H). 13C NMR (-40 °C, 100.6 MHz, C6D5CD3): δ 175.9 (C(tBu)-
CHC(tBu)), 157.2 (C(tBu)CHC(tBu)), 148.6 (C6H3), 146.3 (C6H3),
143.8 (C6H3), 141.1 (C6H3), 138.7 (C6H3), 137.2 (C6H3), 126.6
(C6H3), 126.0 (C6H3), 125.7 (C3H3), 124.6 (C6H3), 123.7 (C6H3),
95.51 (C(tBu)CHC(tBu), JC-H ) 155 Hz), 63.43 (ZrCH2SiMe3,
JC-H ) 103 Hz), 61.58 (ZrCH2SiMe3, JC-H ) 111 Hz), 44.06
(C(CMe3)CHC(CMe3)), 42.48 (C(CMe3)CHC(CMe3)), 30.84,
(C(CMe3)CHC(CMe3)), 30.84, (C(CMe3)CHC(CMe3)), 28.92
(CHMe2), 28.59 (CHMe2), 27.69 (CHMe2), 27.21 (CHMe2), 26.74
(CH3), 26.44 (CH3), 25.41 (CH3), 24.82 (CH3), 24.59 (CH3), 24.36
(CH3), 3.52 (ZrCH2SiMe3). Anal. Calcd for C43H75N2Si2ClZr: C,
64.32; H, 9.41; N, 3.49. Found: C, 63.97; H, 9.03; N, 3.76.
Synthesis of [(NactBu)ZrdNAr(µ2-OTf)]2 (5). In a reac-
tion vessel was dissolved 2 (300 mg, 0.29 mmol) in 50 mL of
toluene, and the solution was cooled to -35 °C. To the cold
solution was slowly added a cold toluene solution (∼15 mL)
containing LiCH2CMe3 (45 mg, 0.58 mmol). After it was
warmed to room temperature, the reaction mixture was stirred
for 1 h. The solution was filtered, and the filtrate was
evaporated under reduced pressure and washed with pentane.
The solid was then dissolved in Et2O, this solution was filtered,
and the filtrate was concentrated and stored at -35 °C for 48
h to afford dark red crystals of [(NactBu)ZrdNAr(µ2-OTf)]2 (5;
156 mg, 0.11 mmol, 76% yield, two crops).
Synthesis of (Nacnac)Zr(OTf)2(η2-OTf) (2). In a reaction
vessel equipped with a stir bar was dissolved (Nacnac)ZrCl3
(1; 800 mg, 1.14 mmol) in THF (20 mL), and the solution was
cooled to -35 °C. To the cold solution was added a cold THF
solution (10 mL) containing AgOTf (940 mg, 3.66 mmol). After
the mixture was stirred for 20 min, the solution was filtered
to remove AgCl, and the filtrate was evaporated under reduced
pressure. The yellow solid was dissolved in dichloromethane,
this solution was filtered, and the filtrate was layered with
pentane. The layered solution was stored at -35 °C for 24 h
to afford yellow crystals of (Nacnac)Zr(OTf)2(η2-OTf) (2; 920
mg, 0.88 mol, 77% yield, three crops).
Data for 2 are as follows. 1H NMR (23 °C, 399.8 MHz, CD2-
Cl2): δ (m, C6H3 and C(tBu)CHC(tBu), 7H), 2.97 (septet,
CH(Me)2, 2H), 2.07 (septet, CH(Me)2, 2H), 1.28 (s, C(tBu)CHC-
(tBu), 18H), 1.19 (d, CHMe2, 6H), 1.13 (d, CHMe2, 6H), 1.07
(d, CHMe2, 6H), 0.81 (d, CHMe2, 6H). 13C NMR (25 °C, 100.6
MHz, CD2Cl2): δ 171.8 (C(tBu)CHC(tBu)), 142.8 (C6H3), 141.6
(C6H3), 140.0 (C6H3), 128.6 (C6H3), 126.6 (C6H3), 125.9 (C6H3),
120.8-116.8 (overlapping m, O3SCF3), 98.65 (C(tBu)CHC(tBu),
JC-H ) 162 Hz), 44.91 (C(CMe3)CHC(CMe3)), 30.35 (C(CMe3)-
CHC(CMe3)), 29.26 (CHMe2), 28.70 (CHMe2), 26.99 (CH3),
26.18 (CH3), 25.65 (CH3), 24.45 (CH3). 19F NMR (23 °C, 399.8
MHz, CD2Cl2): δ -73.8 (q, O3SCF3, JF-F ) 5 Hz), -74.8 (m,
O3SCF3, JF-F ) 5 Hz), -75.7 (q, O3SCF3, JF-F ) 6 Hz). Anal.
Calcd for C38H53N2O9S3F9Zr‚CH2Cl2: C, 41.63; H, 4.92; N, 2.48.
Found: C, 41.17; H, 5.50; N, 2.43.
Synthesis of (Nacnac)Zr(CH2tBu)2Cl (3). In a vial con-
taining 20 mL of Et2O was suspended 1 (300 mg, 0.43 mmol),
and the suspension was cooled to -35 °C. To the cold
suspension was added a cold Et2O solution (∼10 mL) contain-
ing LiCH2CMe3 (67 mg, 0.86 mmol). Upon warming the
mixture was stirred for 30 min, the solution was filtered, and
the filtrate was concentrated and stored at -35 °C for 24 h to
afford yellow crystals of (Nacnac)Zr(CH2tBu)2Cl (3; 286 mg,
0.37 mmol, 86% yield, two crops).
Data for 5 are as follows. 1H NMR (23 °C, 399.8 MHz,
C6D6): δ 7.12-6.80 (m, C6H3 and C(tBu)CHC(tBu)Zr, 7H), 4.35
(septet, CH(Me)2, 1H), 4.13 (septet, CH(Me)2, 1H), 3.56 (septet,
CH(Me)2, 1H), 2.70 (septet, CH(Me)2, 1H), 1.42 (d, CHMe2, 6H),
1.33 (overlap of two d, CHMe2, 6H), 1.28 (C(tBu)CHC(tBu)-
Zr), 9H), 1.12 (d, CHMe2, 3H), 1.03 (overlap of two d, CHMe2,
6H), 0.94 (CHMe2, 3H), 0.91 (C(tBu)CHC(tBu)Zr), 9H).13C
NMR (25 °C, 100.6 MHz, C6D6): δ 248.6 (C(tBu)CHC(tBu)Zr),
192.1 (C(tBu)CHC(tBu)Zr), 145.0 (C6H3), 141.7 (C6H3), 141.3
(C6H3), 141.0 (C6H3), 138.3 (C6H3), 128.5 (C3H3), 127.9 (C3H3),
127.5 (C3H3), 125.5 (C3H3), 124.0 (C3H3), 122.9 (C3H3), 122.3
(C3H3), 120.9 (C(tBu)CHC(tBu)Zr), 120.2 (OSO2CF3), 43.5
(C(CMe3)CHC(CMe3)Zr), 42.11 (C(CMe3)CHC(CMe3)Zr), 30.30
(C(CMe3)CHC(CMe3)Zr), 30.11 (CHMe2), 29.91 (C(CMe3)CHC-
Data for 3 are as follows. 1H NMR (23 °C, 399.8 MHz,
C6D6): δ 7.30-7.10 (m, C6H3, 6H), 6.26 (s, (tBu)CHC(tBu), 1H),
3.66 (br, CH(Me)2, 2H), 2.40 (br, CH(Me)2, 2H), 1.55 (d, CHMe2,
6H), 1.33 (overlap of s and d, ZrCH2CMe3 and CHMe2, 15H),
1.25-1.16 (br, ZrCH2CMe3, C(tBu)CHC(tBu) and ZrCH2CMe3,
31H), 1.01 (br, CHMe2, 6H), 0.81 (br, CHMe2, 6H). 13C NMR
(25 °C, 100.6 MHz, C6D6): δ 176.3 (br, C(tBu)CHC(tBu)), 159.6
(br, C(tBu)CHC(tBu)), 145.9 (br, C6H3), 142.1 (br, C6H3), 138.7
(C6H3), 125.4 (C6H3), 125.1 (C6H3), 95.14 (ZrCH2CMe3, JC-H
104 Hz), 94.43 (C(tBu)CHC(tBu), JC-H ) 157 Hz), 90.90
)