1718
A.J. Nielson, J.M. Waters / Polyhedron 29 (2010) 1715–1726
10.4 Hz, 2H, 2CHs); 3.64 (d, 2JHH 12.8 Hz, 2H, 2CHs); 4.08 (qd, 2JHH
12.8 Hz, 3JHH 4.6 Hz, 2H, 2CHs); 4.27 (m, obsc, 2JHH 12.8 Hz, 2H,
2CHs); 4.30 (dq, obsq, 2JHH 12.8 Hz, 3JHH 7.3 Hz, 2H, 2OCHs); 4.36
(d, 2JHH 12.5 Hz, 2H, 2CHs); 4.68 (dq, 2JHH 12.8 Hz, 3JHH 6.9 Hz,
2H, 2OCHs); 6.82 (d, 4JHH 2.3 Hz, 2H, m-CHs); 6.91 (d, 4JHH
2.3 Hz, 2H, m-CHs); 7.00 (d, 4JHH 2.3 Hz, 2H, m-CHs); 7.17 (d,
4JHH 2.3 Hz, 2H, m-CHs); 7.90 (bt, 3JHH 7.8 Hz, 2H, 2NHs). 13C
NMR d (CDCl3): 15.61 (Me); 19.80 (Mealkoxo); 31.68 (CMe3); 31.71
CMe3); 33.75 (C); 33.81 (C); 45.94 (CH2); 49.27 (CH2); 52.28
(CH2); 52.83 (CH2); 68.41 (OCH2); 122.69 (C); 122.71 (CH); 124.10
(C); 124.51 (C); 124.55 (CH); 124.93 (C); 126.46 (CH); 127.00
(CH); 138 82 (C); 140.30 (C); 157.97 (ipso-C); 160.43 (ipso-C). 1H
NMR d (CDCl3), isomer 2, (30%): 1.28 (s, 18H, 2CMe3); 1.29–1.31
(obsc, 6H, 2Mealkoxo); 1.34 (s, 18H, 2CMe3); 1.69 (s, 6H, 2Mearyl);
2.07 (t, 2JHH 12.2 Hz, 2H, 2CHs); 2.42 (s, 6H, 2Mearyl); 2.51–2.65
(obsc, 2H, 2CHs); 2.67–2.77 (obsc, 2H, 2CHs); 3.04 (p, 3JHH 6.7 Hz,
4JHH 2.3 Hz, 2H, 2CHs); 3.42 (d, 2JHH 11.0 Hz, 2H, 2CHs); 3.44 (m,
2JHH 13.3 Hz, 2H, 2CHs); 3.75 (dq, 2JHH 12.8 Hz, 3JHH 7.0 Hz, 2H,
2OCHs); 4.22–4.39 (obsc, 2H, 2CHs); 4.79 (d, 2JHH 13.0 Hz, 2H,
2CHs); 5.29 (bt, 3JHH 7.5 Hz, 2H, 2NHs); 6.86 (d, 4JHH 2.3 Hz, 2H,
m-CHs); 6.92 (d, 4JHH 2.3 Hz, 2H, m-CHs); 6.97 (d, 4JHH 2.3 Hz,
2H, m-CHs); 7.25 (d, 4JHH 2.3 Hz, 2H, m-CHs). 13C NMR d (CDCl3):
16.78 (2Me); 18.42 (Mealkoxo); 31.68 (obsc,CMe3); 31.71 (ob-
sc,CMe3); 33.75 (C); 33.90 (C); 45.61 (CH2); 48.46 (CH2); 52.53
(CH2); 52.83 (CH2); 58.42 (OCH2); 122.84 (CH); 123.8 (CH); 124.43
(CH); 124.51 (C); 125.12 (C); 125.75 (C); 126.61 (CH); 127.51
(CH); 139.32 (C); 140.80 (C); 157.40 (ipso-C); 159.52 (ipso-C). H2O
(0.06 g, 3.33 mmol) in absolute ethanol (1 mL) was added to the fil-
trate and the solution refluxed for a 1 h giving a further sample of
complex (6). Yield; 0.194 g, 10%. Total yield: 75%. NMR spectroscopy
showed the presence of 78% isomer 1 and 22% isomer 2.
NMR d (CDCl3): 29.62 (CMe3); 31.66 (CMe3); 31.14 (C); 34.88 (C);
51.73 (CH2); 59.23 (CH2); 120.81 (C); 123.04 (CH); 123.26 (CH);
135.69 (C); 140.69 (C); 154.10 (ipso-C).
2.10. [(L6)Ti(OEt)-O-Ti(OEt)(L6)] (7)
Absolute ethanol (30 mL) was added to [Ti(OCHMe2)4] (0.817 g,
2.73 mmol) then N,N-bis(2-hydroxy-3,5-di-tert-butylbenzyl)ethy-
lenediamine, [H2L6], (1.36 g, 2.9 mmol) as for the preparation of
complex (1). The solution was refluxed for 2 h giving a clear yellow
solution to which was added H2O (0.10 g, 5.56 mmol) in absolute
ethanol (1 mL) and the solution refluxed for a further 17 h. On
cooling and standing the complex formed as a yellow solid. Yield:
0.77 g, 47%. C68H110N4O7Ti2 requires C, 68.60; H, 9.31; N, 4.71.
Found: C, 68.55; H, 9.50; N, 4.55%. IR spectrum (nujol),
m :
cmꢁ1
3087w; 1603w; 1441s; 1414m; 1388m; 1375m; 1361m; 1303m;
1274s; 1262s; 1242s; 1203m; 1165m; 1132m; 1097m; 1060m;
1025vw; 1004w; 972vw; 959vw; 932vw; 911w; 886vw; 874w;
869w; 854m; 842m; 804w; 758m; 702bs; 668m; 646vw; 609w;
581m; 569m; 552m; 536m; 488m; 468m; 426m.
CMe3
Me3C
CMe3
Me3C
H
OEt
O
Ti
O
O
Ti
O
N
H
N
N
O
H
N
EtO
H
CMe3
Me3C
CMe3
CMe3
Me3C
Me3C
Me
(7)
Me
H
OEt
Me
O
Ti
O
O
Ti
O
N
2.11. N,N-Dimethyl-N0,N0-bis(2-hydroxy-3-methyl-5-tert-butylbenzyl)
ethylenediamine, H2L7
H
N
N
O
H
N
Methanol (35 mL) was added to N,N-dimethylethylenediamine
(4.38 g. 0.05 mol) and the rapidly stirred solution cooled to 0 °C
after which aqueous formaldehyde solution (8 mL, 0.1 mol) was
added dropwise. The mixture was stirred for 2 h, then 4-tert-bu-
tyl-2-methylphenol (16.31 g, 0.1 mol) was added and the mixture
was refluxed for 23 h. On cooling the product separated as an oil
which solidified on standing at ꢁ20 °C. Yield: 13.7 g, 63%.
C28H44N2O2 requires C, 76.32; H, 10.07; N, 6.36. Found: C, 76.67;
EtO
H
Me
CMe3
Me3C
(6)
H, 10.45; N, 6.36%. IR spectrum (nujol)
m
cmꢁ1: 3056bs; 1608w;
1487s; 1462s; 1376s; 1362s; 1341m; 1310m; 1288m; 1254m;
1235s; 1217s; 1169; 1117m; 1104m; 1058w; 1044w; 1019w;
989m; 962w; 933w; 917w; 876m; 814m; 784m; 748w; 734w;
681w; 666w; 630w; 609w; 578w; 514w; 500w; 414w. 1H NMR d
(CDCl3): 1.37 (s, 18H, CMe3); 2.32 (s, 6H, 2Me); 2.39 (s, 6H,
2Me); 2.65 (s, 4H, 2CH2); 3.70 (s, 4H, 2CH2); 7.00 (d, 4JHH 2.4 Hz,
2H, m-Hs); 7.18 (d, 4JHH 2.4 Hz, 2H, m-Hs); 9.30 (b, 2H, 2OH).
13C NMR d (CDCl3): 16.82 (Me); 32.19 (CMe3); 34.50 (C); 45.52
(NMe); 49.74 (CH2); 57.01 (CH2); 122.01 (C); 125.09 (C); 125.31
(CH); 127.96 (CH); 141.49 (C); 153.18 (ipso-C).
2.9. N,N-Bis(2-hydroxy-3,5-di-tert-butylbenzyl)ethylenediamine, H2L6
Ethanol (60 cm3) was added to ethylenediamine (2.91 g,
0.049 mol) and the mixture cooled to 0 °C and stirred rapidly while
aqueous formaldehyde (7.86 cm3) was added dropwise. After stir-
ring for 15 min with the ice bath removed, 2,4-di-tert-butylphenol
(20.0 g, 0.097 mol) was added in batches and the mixture was re-
fluxed for 18 h. On cooling and standing for several days a white
solid was formed which were repeatedly recrystallised from hot
ethanol until NMR spectroscopy indicated a pure product was ob-
tained. Yield: 4.37 g, 18%. C32H52N2O2 requires C, 77.36; H, 10.55;
N, 5.64. Found: C, 77.98; H, 10.80; N, 5.60%. 1H NMR d (CDCl3):
1.36 (s, 18H, 2CMe3); 1.51 (s, 18H, 2CMe3); 3.08 (s, 4H, 2CH2);
3.99 (s, 4H, 2CH2); 6.92 (d, 3JHH 2.4 Hz, 2H, m-Hs); 7.31 (d, 3JHH
2.4 Hz, 2H, m-Hs); 10.78 (b, 2H, NHs), OHs not observed. 13C
2.12. [(L7)Ti(OEt)–O–Ti(OEt)(L7)] (8)
Absolute ethanol (30 mL) was added to titanium isopropoxide
(1.048 g, 3.56 mmol) then finely powdered N,N-dimethyl-N0,
N0-bis(2-hydroxy-3-methyl-5-tert-butylbenzyl)ethylenediamine,