2932
P. Elo et al. / Journal of Organometallic Chemistry 694 (2009) 2927–2933
= 169.5 (C@N), 168.1 (C@N), 168.9 (C@O), 156.5 (C@O), 148.3 (–N-
Ar), 148.2 (–N-Ar), 129.1 (Ar), 127.8 (Ar), 126.9 (Ar), 125.1 (Ar),
123.5 (Ar), 121.2 (Ar), 75.5 [–(CO)–CH–(CN)–], 65.2 (–O–CH2–),
62.8 (–O–CH2–), 62.2 (–O–CH2–), 61.2 (–O–CH2–), 36.6 [–(CO)–
CH–(CN)–], 14.3 (CH3), 14.2 (CH3), 14.1 (CH3), 14.0 (CH3) Anal. Calc.
for C26H32N2O6TiCl2: C, 53.17; H, 5.49; N, 4.77; found C 53.01; H,
5.38; N, 4.61.
302 K): d = 7.05–6.82 (m, 6H, Ar); 6.82–6.72 (m, 2H, Ar); 4.72 (s,
1H, –(CO)–CH–(CN)–); 4.27 (q, 2H, –O–CH2-Me); 4.16 (q, 2H, –O–
CH2-Me); 3.96 (m, 3H, –O–CH2-Me); 3.54 (m, 1H, –O–CH2-Me)
3.19 (s, 1H –(CO)–CH–(CN)–); 1.35 (t, 3H, –CH3,); 1.27 (t, 3H,
–CH3); 1.15 (t, 3H, –CH3); 1.10 (t, 3H, –CH3) 13C{1H NMR}(CDCl3,
50.3 MHz, 302 K): d = 170.8 (C@N), 169.4 (C@O), 167.5 (C@N),
163.2 (Ar-F), 161.5 (Ar-F), 158.4 (Ar-F), 157.1 (Ar-F), 156.9 (C@O),
144.0 (N-Ar), 143.7(N-Ar), 139.2 (N-Ar), 139.1 (N-Ar), 122.5 (Ar),
122.0 (Ar), 116.3 (Ar), 115.9(Ar), 115.6 (Ar), 115.5 (Ar), 115.1 (Ar),
114.8 (Ar), 70.8 [–(CO)–CH–(CN)–], 65.5 (–O–CH2–), 62.5 (–O–
CH2–), 62.3 (–O–CH2–), 61.4 (–O–CH2–), 36.4 [–(CO)–CH–(CN)–],
14.2 (CH3), 14.2 (CH3), 14.1 (CH3), 14.0 (CH3) Anal. Calc. for
C26H30N2O6F2ZrCl2: C, 46.84, H 4.54, N, 4.20; found C, 46.95; H,
4.63; N, 4.14.
4.5. Preparation of [EtOC(O)CHC(N(p-F-Ph)EtO]2TiCl2 2Ti
Complex 2Ti was prepared by a similar method to that described
for 1Ti with yield of 29%. 1H NMR (CDCl3, 200 MHz, 302 K):
d = 7.08–6.79 (m, 6H, Ar); 6.82–6.72 (m, 2H, Ar); 4.15 (s, 1H,
–(CO)–CH–(CN)–); 4.25 (q, 2H, –O–CH2-Me); 4.16 (q, 2H, –O–CH2-
Me); 3.94 (m, 3H, –O–CH2-Me); 3.49 (m, 1H, –O–CH2-Me) 3.18 (s,
1H-(CO)–CH–(CN)–); 1.32 (t, 3H, –CH3); 1.25 (t, 3H, –CH3); 1.15 (t,
3H, –CH3); 1.11 (t, 3H, –CH3) 13C{1H NMR}(CDCl3, 50.3 MHz,
302 K): d = 170.6 (C@N), 169.9 (C@O), 167.8 (C@N), 163.0 (Ar-F),
161.6 (Ar-F), 158.2 (Ar-F), 157.2 (Ar-F), 156.9 (C@O), 144.2 (N-Ar),
143.7(N-Ar), 139.2 (N-Ar), 139.0 (N-Ar), 122.5 (Ar), 122.2 (Ar),
116.4 (Ar), 115.9(Ar), 115.8 (Ar), 115.4 (Ar), 115.2 (Ar), 114.8 (Ar),
70.2 [–(CO)–CH–(CN)–], 65.3 (–O–CH2–), 62.4 (–O–CH2–), 62.1
(–O–CH2–), 61.5 (–O–CH2–), 36.5 [–(CO)–CH–(CN)–], 14.2 (CH3),
14.1 (CH3), 14.1 (CH3), 14.0 (CH3) Anal. Calc. for C26H30N2O6F2TiCl2:
C, 50.10; H, 4.85; N, 4.49; found C, 49.81; H, 4.78; N, 4.38.
4.9. X-ray Crystallographic Study of 1Zr
The single-crystal X-ray diffraction study of 1Zr was carried out
on a Bruker–Nonius Kappa-CCD diffractometer at 123(2) K using
Mo K
used for structure solution, and full-matrix least-squares refine-
ment on F2
SHELXL-97). [39] H atoms were localized by difference
a radiation (a = 0.71073 Å). Direct Methods (SHELXS-97) were
(
Fourier synthesis and refined using a riding model. A semi-empir-
ical absorption correction was applied.
1Zr: yellow crystals, C27H32Cl2N2 O6Zr – 0.5 C7H8, M = 676.72,
crystal size 0.36 ꢂ 0.20 ꢂ 0.04 mm, monoclinic, space group P21/n
(No. 14): a = 12.204(2) Å, b = 14.905(3) Å, c = 17.401(4) Å, b =
4.6. Preparation of [EtOC(O)CHC(N(p-Me-Ph)EtO]2TiCl2 3Ti
90.65(2)
F(0 0 0) = 1396,
5572 unique [Rint = 0.080], 328 parameters, 19 restraints, R1
V = 3165.0(11) Å3,
= 0.559 mmꢀ1
Z = 4,
q ,
(calc.) = 1.420 Mg mꢀ3
Complex 3Ti was prepared by a similar method to that de-
scribed for 1Ti with yield of 34%. 1H NMR (CDCl3, 200 MHz,
302 K): d = 6.98–6.81 (m, 6H, Ar); 6.61–6.69 (m, 2H, Ar); 4.17 (s,
1H, –(CO)–CH–(CN)–); 4.25 (q, 2H, –O–CH2–Me); 4.18 (q, 2H, –
O–CH2-Me); 3.92 (m, 3H, –O–CH2-Me); 3.52 (m, 1H, –O–CH2-Me)
3.20 (s, 1H –(CO)–CH–(CN)–); 1.33 (t, 3H, –CH3); 1.24 (t, 3H,
–CH3); 1.15 (t, 3H, –CH3); 1.11 (t, 3H, –CH3) 13C{1H NMR}(CDCl3,
50.3 MHz, 302 K): d = 169.4 (C@N), 168.0 (C@N), 168.8 (C@O),
156.8 (C@O), 145.7 (–N-Ar), 145.3 (–N-Ar), 134.5 (Ar-Me), 132.4
(Ar), 129.7 (Ar), 129.6 (Ar), 126.2 (Ar), 120.7 (Ar), 75.6 [–(CO)–
CH–(CN)–], 65.2 (–O–CH2–), 62.7 (–O–CH2–), 61.8 (–O–CH2–),
61.2 (–O–CH2–), 36.4 [–(CO)–CH–(CN)–], 20.9 (Ar-CH3), 20.7 (Ar-
CH3), 14.2 (CH3), 14.1(7) (CH3), 14.1(1) (CH3), 14.0(CH3) Anal. Calc.
for C28H36N2O6TiCl2: C, 54.65; H, 5.90; N, 4.55; found C, 54.80; H,
5,98; N, 4.50.
q
, 36922 reflexes (2hmax = 50°),
(I > 2r(I)) = 0.045, wR2 (all data) = 0.106, GooF = 1.06, largest diff.
peak and hole 0.697 and ꢀ0.526e Åꢀ3
.
Acknowledgements
Financial support for this work from Academy of Finland, Pro-
jects 209739 and 123248 is greatly acknowledged. Warm thanks
to Doctor Sami Hietala and Sirpa Vuorinen for the help with dy-
namic NMR measurements. Warm thanks also to Sami Lipponen
for the help with GPC measurements of the polymer products.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
CCDC 716356 contains the supplementary crystallographic data
for complex 1Zr. These data can be obtained free of charge from
4.7. Preparation of [EtOC(O)CHC(NPh)EtO]2ZrCl2 1Zr
Complex 1Zr was prepared by a similar method to that de-
scribed for 1Ti with yield of 36%. 1H NMR (CDCl3, 200 MHz,
302 K): d = 7.29–7.20 (m, 2H, Ar); 7.05–6.92 (m, 6H, Ar); 6.86–
6.74 (m, 2H, Ar); 4.72 (s, 1H, –(CO)–CH–(CN)–); 4.27 (q, 2H, –O–
CH2–Me); 4.16 (q, 2H, –O–CH2-Me); 3.96 (m, 3H, –O–CH2-Me);
3.48 (m, 1H, –O–CH2-Me) 3.22 (s, 1H–(CO)–CH–(CN)–); 1.35 (t,
3H, –CH3,); 1.27 (t, 3H, –CH3); 1.14 (t, 3H, –CH3); 1.10 (t, 3H,
–CH3) 13C{1H NMR}(CDCl3, 50.3 MHz, 302 K): d = 170.1 (C@N),
168.4 (C@N), 156.5 (C@O), 156.4 (C@O), 148.3 (–N-Ar), 148.2
(–N-Ar), 129.1 (Ar),129.0 (Ar), 128.1 (Ar), 125.2 (Ar), 123.5 (Ar),
121.2 (Ar), 70.1 [–(CO)–CH–(CN)–], 65.0 (–O–CH2–), 62.2 (–O–
CH2–), 62.1 (–O–CH2–), 61.2 (–O–CH2–), 36.7 [–(CO)–CH–(CN)–],
14.2 (CH3), 14.1(8) (CH3), 14.1(1) (CH3), 14.0 (CH3) Anal. Calc. for
C26H32N2O6ZrCl2: C, 49.52; H, 5.11; N, 4.44; found C, 49.81; H,
5.26; N, 4.36.
References
[1] S.D. Ittel, L.K. Johnson, M. Brookhart, Chem. Rev. 100 (2000) 1169.
[2] G.J.P. Britovsek, V.C. Gibson, D.F. Wass, Angew. Chem. Int. Ed. 38 (1999) 428.
[3] V.C. Gibson, S.K. Spitzmesser, Chem. Rev. 103 (2003) 283.
[4] R. Furuyama, T. Fujita, S.F. Funaki, T. Nobori, T. Nagata, K. Fujiwara, Catal. Surv.
Asia 8 (2004) 61.
[5] H. Makio, N. Kashiwa, T. Fujita, Adv. Synth. Catal. 344 (2002) 477.
[6] L. Bourget-Merle, M.F. Lappert, J.R. Severn, Chem. Rev. 102 (2002) 3031.
[7] C. Qi, S. Zhang, J. Sun, J. Organomet. Chem. 690 (2005) 2941.
[8] M. Tamm, S. Randoll, E. Herdtweck, N. Kleigrewe, G. Kehr, G. Erker, B. Rieger,
Dalton Trans. (2006) 459.
´
[9] M. Sanz, M.E.G. Mosquera, T. Cuenca, C. Ramırez de Arellano, B.M. Schormann,
B. Bochmann, Polyhedron 26 (2007) 5339.
[10] M. Zhou, H. Tong, X. Wei, D. Liu, J. Organomet. Chem. 692 (2007) 5195.
[11] R.K.J. Bott, M. Hammond, P.N. Horton, S.J. Lancaster, M. Bochmann, P. Scott,
Dalton Trans. (2005) 3611.
[12] M.J. Ferreira, I. Matos, T. Duarte, M. Marques, A.M. Martins, Catal. Today 647
(2008) 122.
4.8. Preparation of [EtOC(O)CHC(N(p-F-Ph)EtO]2ZrCl2 2Zr
Complex 2Zr was prepared by a similar method to that de-
scribed for 1Ti with yield of 32%. 1H NMR (CDCl3, 200 MHz,