G. Giambastiani et al.
phase was washed with EtOAc (3ꢂ10 mL). The collected organic ex-
tracts were dried over Na2SO4, and the solvent was evaporated under re-
duced pressure to give a crude yellow oil. The pure product was finally
precipitated from cold hexane (ꢀ208C) in the form of pure yellow crys-
ꢀ308C, thus yielding pale-yellow and white crystals, respectively, suitable
for X-ray diffraction analyses (94% yield of the isolated products). Com-
plexes 15 and 16 were obtained as pale-yellow oils, and all attempts to
isolate crystals failed. However, both complexes were analytically pure
with no traces of residual reagents/solvents. These oils were dried under
vacuum to constant weight.
tals. The latter were separated by filtration and washed with cold hexane
3
(0.295 g, 93.6%). 1H NMR (300 MHz, CD2Cl2, 293 K): d=1.20 (d, JHH
=
1
6.8 Hz, 12H; CH
ACHTUNGTRENNUNG
13: (96% yield of isolated product); H NMR (300 MHz, CD2Cl2, 293 K):
3.00 (sept, 3JHH =6.8 Hz, 2H; CH
AHCTUNGTRENNUNG
ACTHNUTRGNEUNG
d=1.06 (d, 3JHH =6.9 Hz, 6H; CH(CH3ACH3B); H19, H22), 1.16 (d,
3JHH =6.9 Hz, 6H; CH
H23, H24, H25), 3.50 (sept, 3JHH =6.9 Hz, 2H; CH
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG(CH3)2;
H8), 7.11–7.15 (m, 1H; CH Ar; H15), 7.19–7.21 (2H; CH Ar; H14,
H16), 7.61 (m, 1H; CH Ar; H9), 7.65–7.66 (2H; CH Ar; H2, H3), 7.94–
7.96 (m, 1H; CH Ar; H4), 8.06 (m, 1H; H6), 8.26 ppm (s, 1H; CHN;
H11); 13C(1H) NMR (75 MHz, CD2Cl2, 293 K): d=12.3 (C10), 23.1 (CH-
4.44 (s, 2H; CH2N; H10), 6.48 (m, 1H; CH Ar; H8), 7.12–7.15 (4H; CH
Ar; H2, H13, H14, H15), 7.38 (t, 3JHH =7.8 Hz, 1H; CH Ar; H3), 7.47
(m, 1H; CH Ar; H6), 7.60 (m, 1H; CH Ar; H4), 7.70 (m, 1H; CH Ar;
H7), 7.85 ppm (m, 1H; CH Ar; H9); 13C{1H} NMR (75 MHz, CD2Cl2,
ACHTUNGTRENNUNG(CH3)2; C19, C20, C22, C23), 27.9 (CHAHCTUNGTRENN(UNG CH3)2; C18, C21), 107.2 (C8),
122.9 (C14, C16), 124.1 (C6, C15), 127.1 (C2), 127.4 (C4), 129.4 (C3),
137.1 (C5), 137.4 (C13, H17), 138.8 (C7), 140.0 (C9), 140.6 (C1), 149.0
(C12), 161.1 ppm (C11); elemental analysis (%) calcd for C23H27N3
(345.48): C 79.96, H 7.88, N 12.16; found: C 80.00, H 7.93, N 12.07.
293 K): d=24.0 (CH
N
(CH3ACH3B); C19,
ACHTUNGTRENNUNG
C22), 27.7 (CH(CH3)2; C17, C20), 41.0 (NACTHUNGTRENNUNG
R
(C10), 107.3 (C8), 117.7 (C4), 120.1 (C6), 123.7 (C13, C15), 124.9 (C14),
126.5 (C9), 127.6 (C2), 129.1 (C3), 140.7 (C7), 142.7 (C), 143.0 (C), 144.0
(C), 147.8 ppm (C12, C16); elemental analysis (%) calcd for C28H44N6Zr
(555.91): C 60.49, H 7.98, N 15.12; found: C 60.52, H 8.03, N 15.10.
Synthesis of 2,6-diisopropyl-N-[3-(5-methyl-1H-pyrazol-1-yl)benzyl]ani-
line (H2LMe
)
(12): NaBH3CN (0.06 g, 1.02 mmol) and acetic acid
(0.06 mL, 1.02 mmol) were added in se-
quence to a cooled solution (08C) of 11
(0.295 g, 0.85 mmol) in dry, degassed
MeOH/THF (1:1, 5 mL). The resulting
mixture was maintained under stirring
and in an inert atmosphere at room tem-
perature for 1 h. Afterwards, saturated
Na2CO3 and water (1:1) were added, the
organic phase was separated, and the
aqueous layer was extracted with EtOAc
(3ꢂ10 mL). The collected organic layers
were dried over Na2SO4, and the solvent
1
14: (94% yield of isolated product); H NMR (300 MHz, CD2Cl2, 293 K):
ACTHNUTRGNEUNG
d=1.05 (d, 3JHH =6.9 Hz, 6H; CH(CH3ACH3B); H19, H22), 1.17 (d,
3JHH =6.9 Hz, 6H; CH
N
ACHTUNGTRENNUNG(CH3)2;
H23, H24, H25), 3.52 (sept, 3JHH =6.9 Hz, 2H; CH
AHCTUNGTRENNUNG
4.50 (s, 2H; CH2N; H10), 6.48 (m, 1H; CH Ar; H8), 7.10–7.14 (4H; CH
Ar; H2, H13, H14, H15), 7.38 (t, 3JHH =7.8 Hz, 1H; CH Ar; H3), 7.44
(m, 1H; CH Ar; H6), 7.70 (m, 1H; CH Ar; H4), 7.70 (m, 1H; CH Ar;
H7), 7.84 ppm (m, 1H; CH Ar; H9); 13C{1H} NMR (75 MHz, CD2Cl2,
293 K): d=24.0 (CH
N
(CH3ACH3B); C19,
ACHTUNGTRENNUNG
H22), 27.7 (CH(CH3)2; C17, H20), 40.6 (NACTHUNGTRENNUNG
E
(C10), 107.3 (C8), 117.7 (C4), 120.2 (C6), 123.7 (C13, H15), 125.0 (C14),
126.5 (C9), 127.6 (C2), 129.1 (C3), 140.0 (C), 140.7 (C7), 142.6 (C), 143.9
(C), 147.9 (C12, H16); elemental analysis (%) calcd for C28H44N6Hf
(643.18): C 52.29, H 6.90, N 13.07; found: C 52.34, H 6.95, N, 13.00.
was evaporated under reduced pressure. The crude residue was purified
by flash chromatography on silica gel with petroleum ether/EtOAc
(83:17) as the eluent to give the pure product 12 as a colorless oil
(0.272 g, 92.0%). 1H NMR (300 MHz, CD2Cl2, 293 K): d=1.30 (d, JHH
=
3
1
15: (95% yield of isolated product); H NMR (400 MHz, CD2Cl2, 293 K):
6.8 Hz, 12H; CH
3.33–3.45 (3H; CHACHTUNGTRENNUNG
H11), 6.28 (m, 1H; CH; H8), 7.12–7.21 (3H; CH Ar; H14, H15, H16),
7.43–7.54 (3H; CH Ar; H2, H3, H4), 7.61–7.63 ppm (2H; CH Ar; H9,
H6); 13C{1H} NMR (75 MHz, CD2Cl2, 293 K): d=12.3 (C10), 24.1 (CH-
ACHTUNGTRENNUNG
ACTHNUTRGNEUNG
d=1.02 (d, 3JHH =6.9 Hz, 6H; CH(CH3ACH3B); H19, H22), 1.17 (d,
3JHH =6.9 Hz, 6H; CH
2.79 (brs, 18H; N
(CH3)2; H23, H24, H25), 3.48 (sept, 3JHH =6.9 Hz, 2H;
CH(CH3)2; H17, H20), 4.51 (s, 2H; CH2N; H10), 6.18 (m, 1H; CH Ar;
(CH3ACH3B); H18, H21), 2.19 (s, 3H; CH3; H26),
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
H8), 7.11 (brs, 3H; CH Ar; H13, H14, H15), 7.18 (brs, 1H; CH Ar; H6),
7.26 (m, 1H; CH Ar; H2), 7.33 (m, 1H; CH Ar; H4), 7.39–7.44 (1H; CH
Ar; H3), 7.52 ppm (m, 1H; CH Ar; H7). 13C{1H} NMR (100 MHz,
CD2Cl2, 293 K): d 12.0 (CH3; C26), 24.0 (CH
24.9 (CH (CH3)2; C17, C20), 41,1 (N-
(CH3ACH3B); C19, C22), 27.7 (CH
AHCTUNTGREG(NNNU CH3); C23, C24, C25), 60.0 (C10), 106.6 (C8), 123.0 (C4), 123.7 (C13,
C15), 125.0 (C14), 125.7 (C6), 128.2 (C2), 128.7 (C3), 138.5 (C9), 139.4
(C7), 139.8 (C), 142.2 (C), 143.5 (C), 147.8 ppm (C12, C16); elemental
analysis (%) calcd for C29H46N6Zr (569.94): C 61.11, H 8.14, N 14.75;
found: C 61.15, H 8.17, N 14.71.
ACHTUNGTRENNUNG(CH3)2; C19, C20, C22, C23), 27.7 (CHAHCTUNGTRENN(UNG CH3)2; C18, C21), 55.6 (C11),
106.9 (C8), 123.4 (C2), 123.6 (C14, C16), 124.0 (C6), 124.2 (C15), 126.8
(C4), 129.0 (C3), 138.7 (C7), 139.6 (C9), 140.2 (C1), 141.6 (C12), 142.7
(C5), 143.0 ppm (C13, C17); elemental analysis (%) calcd for C23H29N3
(347.50): C 79.50, H 8.41, N 12.09; found: C 79.55, H 8.43, N 12.02.
General procedure for the synthesis of complexes [ZrIV
G
(CH3ACH3B); C18, C21),
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
A
E
U
1
16: (91% yield of isolated product); H NMR (400 MHz, CD2Cl2, 293 K):
ACTHNUTRGNEUNG
d=0.97 (d, 3JHH =6.9 Hz, 6H; CH(CH3ACH3B); H19, H22), 1.13 (d,
3JHH =6.9 Hz, 6H; CH
2.77 (brs, 18H; N
(CH3)2; H23, H24, H25), 3.45 (sept, 3JHH =6.9 Hz, 2H;
CH(CH3)2; H17, H20), 4.50 (s, 2H; CH2N; H10), 6.14 (m, 1H; CH Ar;
(CH3ACH3B); H18, H21), 2.13 (s, 3H; CH3; H26),
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
H8), 7.07 (brs, 3H; CH Ar; H13, H14, H15), 7.11 (brs, 1H; CH Ar; H6),
7.19 (m, 1H; CH Ar; H2), 7.29 (m, 1H; CH Ar; H4), 7.35–7.39 (1H; CH
Ar; H3), 7.48 ppm (m, 1H; CH Ar; H7); 13C{1H} NMR (100 MHz,
CD2Cl2, 293 K): d=12.0 (CH3; C26), 24.0 (CH
24.9 (CH (CH3)2; C17, C20), 40.6 (N-
(CH3ACH3B); C19, C22), 27.7 (CH
(CH3); C23, C24, C25), 59.5 (C10), 106.6 (C8), 123.1 (C4), 123.7 (C13,
C15), 125.0 (C14), 125.7 (C6), 128.7 (C2), 128.8 (C3), 138.5 (C9), 139.4
(C7), 139.8 (C), 142.1 (C), 143.5 (C), 147.9 ppm (C12, C16); elemental
analysis (%) calcd for C29H46N6Hf (657.21): C 53.00, H 7.05, N 12.79;
found: C 53.07, H 7.11, N 12.82.
(CH3ACH3B); C18, C21),
ACHTUNGTRENNUNG
G
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
(15), and [HfIV
gands H2L 4 or H2LMe 12 (1 mmol) in dry and degassed benzene (4 mL)
was treated dropwise with a solution of the proper metal precursor ([MIV
(NMe2)4] 99%; M=Zr, Hf; 1.05 equiv) in benzene (3 mL). The reaction
mixture was maintained under stirring at room temperature for 20 h and
then concentrated in vacuo to afford semisolid pale-yellow crude materi-
als. The purification of 13 and 14 was conveniently achieved by crystalli-
zation from concentrated solutions of the complexes in pentane cooled at
ACHTUNGTRENNUNG )ACHTUNGTREG(NUNN NMe2)3] (16): A solution of the selected li-
(k-N-HLMe
-
ACHTUNGTRENNUNG
General procedure for the synthesis of complexes [ZrIV(k3-N,C,N-L)-
ACHUTNGRENNUG CAHTUNGTRENNUGN
(NMe2)2] (17), [HfIV(k3-N,C,N-L)(NMe2)2] (18), [ZrIV(k-N,C,N-LMe)-
A
)ACTHUNGETRN(NUG NMe2)2] (20): A solution of the
&
12
&
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
ÝÝ
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