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Can. J. Chem. Vol. 86, 2008
6H), 2.02 (s, 12H). 13C (CDCl3, 125.679 MHz) δ: 146.9,
139.4, 137.8, 135.9, 130.9 (d), 129.1 (d), 128.6 (d), 21.4 (q),
20.8 (q). 11B (CDCl3, 128.370 MHz) δ: 29.30. IR (nujol
mull) ν: 3668 (w), 3652 (w), 3646 (w), 3539 (br), 3417 (w),
1729 (w), 1613 (m), 1584 (m), 1561 (m), 1360 (s), 1309
(vs), 1261 (m), 1150 (w), 1112 (m), 1094 (m), 1087 (m),
1048 (m), 1038 (m), 848 (s), 811 (m), 759 (s), 742 (m), 666
(w), 656 (w). Anal. calcd. for C24H27BO2: C, 80.46; H, 7.60.
Found: C, 80.37; H, 7.49.
(C6D6, 499.768 MHz) δ: 7.62 (t, J = 7.5 Hz, 1H), 7.22 (d,
J = 7.5 Hz, 2H), 7.03 (s, 4H), 2.42 (s, 6H), 2.18 (s, 12H),
0.00 (s, 18H). (This molecule was not isolated as an analyti-
cally pure compound).
[Ge(OC6H3Mes2)2] (10)
Under an inert atmosphere, a solution of Ge[N(SiMe3)2]2
(0.24 g, 0.61 mmol) in 2 mL hexanes was added dropwise to
a suspension of 2,6-bis(2,4,6-trimethylphenyl)phenol 1
(0.20 g, 0.61 mmol) in 5 mL anhyd. hexanes. After 45 min,
the solvent was decanted from a white precipitate. Yield =
0.16 g (72%); mp = 318–319 °C. 1H NMR (CD2Cl2,
499.767 MHz) δ: 6.81–6.88 (m, 3H), 6.75 (s, 4H), 2.29 (s,
6H), 1.79 (s, 12H). 13C NMR (CD2Cl2, 125.678 MHz) δ:
138.1, 136.2, 129.5, 129.2, 128.8, 128.5, 119.2, 21.0, 20.1.
IR (nujol mull) ν: 1610 (w), 1585 (w), 1484 (m), 1414 (s),
1260 (s), 1230 (vs), 1091 (m), 1071 (s), 1016 (m), 948 (w),
845 (vs), 799 (m), 754 (s), 739 (w), 728 (w), 670 (m), 659
(s), 609 (m). Anal. calcd. for C48H50GeO2: C, 78.81; H,
6.89. Found: C, 79.14; H, 7.08.
Synthesis of metal complexes
[Me2Al(µ-OC6H3Mes2)]2 (7)
Under an inert atmosphere, AlMe3 (1.01 mL, 2.0 mol/L in
hexanes) was added dropwise to a solution of 2,6-bis(2,4,6-
trimethylphenyl)phenol 1 (0.56 g, 1.69 mmol) in 10 mL
anhyd. CH2Cl2. After stirring for 5 min at RT, the solution
was concentrated under vacuum and then cooled to –30 °C.
The next day, the solution was decanted from colorless crys-
1
tals. Yield = 0.25 g (38%); mp = 238–240 °C. H NMR
(C6D6, 499.767 MHz) δ: 6.85 (s, 4H), 6.69 (t, J = 7 Hz, 1H),
6.59 (d, J = 7 Hz, 2H), 2.19 (s, 6H), 2.15 (s, 12H), –1.26 (s,
6H). 13C NMR (C6D6, 125.680 MHz) δ: 138.3, 137.9, 135.9,
133.1, 129.5, 129.3, 128.3, 21.9, 21.7. IR (nujol mull) ν:
1610 (w), 1405 (m), 1261 (w), 1190 (m), 1182 (m), 1091
(m), 1032 (w), 848 (m), 825 (m), 803 (w), 774 (w), 758 (w),
701 (s), 635 (m). Anal. calcd. forC52H62Al2O2, C, 80.80; H,
8.08. Found: C, 81.14; H, 8.18.
[(Me2N)2Ti(OC6H3Mes2)2] (11)
Under an inert atmosphere, a solution of Ti(NMe2)4
(0.26 g, 1.15 mmol) in 5 mL anhyd. CH2Cl2 was added
dropwise to a solution of 2,6-bis(2,4,6-trimethylphenyl)phe-
nol 1 (0.76 g, 2.30 mmol) in 10 mL anhyd. CH2Cl2. The so-
lution was allowed to stir for 10 min at RT and then cooled
to –30 °C. After 3 h, the solution was decanted from orange
1
crystals. Yield = 0.59 g (64%); mp 180 °C (dec.). H NMR
[Sn(OC6H3Mes2)2] (8)
(C6D6, 400.137 MHz) δ: 6.82–6.87 (m, 7H), 2.30 (s, 6H),
2.24 (s, 6H), 2.11 (s, 12H). 13C NMR (C6D6, 100.624 MHz)
δ: 160.2, 137.3, 136.7, 135.6, 131.1, 130.5, 128.3, 120.2,
43.8, 21.0, 20.9. IR (nujol mull) ν: 3279 (m), 1611 (m),
1580 (m), 1484 (m), 1413 (vs), 1345 (m), 1251 (vs), 1229
(vs), 1146 (m), 1083 (s), 1054 (m), 1029 (m), 1008 (m), 950
(s), 904 (m), 876 (vs), 849 (vs), 799 (m), 778 (m), 757 (vs),
741 (w), 691 (vs), 679 (s), 597 (s). Anal. calcd. for
C52H62N2O2Ti: C, 78.57; H, 7.86; N, 3.52. Found: C, 78.20;
H, 7.83; N, 3.37.
Under an inert atmosphere, a solution of Sn[N(SiMe3)2]2
(0.33 g, 0.76 mmol) in 2 mL anhyd. benzene was added
dropwise to a solution of 2,6-bis(2,4,6-trimethylphenyl)phe-
nol 1 (0.50 g, 1.51 mmol) in 10 mL anhyd. benzene. The
mixture was allowed to stir for 3 h at RT and then filtered.
Slow evaporation of the solvent gave a yellow solid that was
recrystallized from warm hexanes to give colorless crystals:
1
Yield = 0.48 g (81%); mp = 321–322 °C. H NMR (CD2Cl2,
499.767 MHz) δ: 6.84 (d, J = 6.9 Hz, 2H), 6.79 (s, 4H), 6.73
(t, J = 6.9 Hz, 1H), 2.29 (s, 6H), 1.82 (s, 12H). 13C NMR
(100.624 MHz, C6D6) δ: 157.8, 138.5, 137.8, 137.4, 129.7,
129.5, 129.2, 117.9, 21.1, 20.5. 119Sn{1H} (CD2Cl2,
223.867 MHz) δ: -344.23. IR (nujol mull) ν: 1610 (m), 1584
(m), 1412 (s), 1262 (m), 1246 (s), 1088 (w), 1072 (m), 1031
(br), 844 (vs), 798 (w), 787 (w), 752 (m), 739 (w), 649 (m).
Anal. calcd. for C48H50O2Sn: C, 74.14; H, 6.48. Found: C,
74.03; H, 6.39.
Crystallographic studies2
The crystal was mounted on a glass fibre (1, 10) or on the
top of the nylon fibre of a CryoLoop™ (diameter of the ny-
lon fibre: 10 microns (1 micron = 1 µm); loop diameter =
0.2–0.3 mm; Hampton Research, USA) (5–8, 11). Data were
collected at the temperature indicated in Table 1 on a Nonius
Kappa-CCD diffractometer using monochromated Mo Kα
radiation (λ = 0.71073 Å) with COLLECT (40). The unit-
cell parameters were calculated and refined from the full
data set. Crystal cell refinement and data reduction were car-
ried out using DENZO (41). The data were scaled using
SCALEPACK (41). The structures were solved by direct
methods using SHELXTL-NT V6.1 suite of programs (42)
(1, 6, 8, 10) or SIR-97 (43) (5, 7, 11). All of the non-
[(Me3Si)2NGe(OC6H3Mes2)] (9)
Under an inert atmosphere, a solution of Ge[N(SiMe3)2]2
(0.57 g, 1.45 mmol) in 2 mL CH2Cl2 was added dropwise to
a solution of 2,6-bis(2,4,6-trimethylphenyl)phenol 1 (0.48 g,
1.45 mmol) in 5 mL anhyd. CH2Cl2. After 5 min, the solvent
was removed under vacuum, and the crude product was
recrystallized from benzene. Mp = 84–86 °C. 1H NMR
2 Supplementary data for this article are available on the journal Web site (canjchem.nrc.ca) or may be purchased from the Depository of Un-
published Data, Document Delivery, CISTI, National Research Council Canada, Ottawa, ON K1A 0R6, Canada. DUD 5242. For more in-
formation on obtaining material, refer to cisti-icist.nrc-cnrc.gc.ca/irm/unpub_e.shtml. CCDC 618683, 618675, 652069, 618680, 618685,
618681, and 618686 contain the crystallographic data for this manuscript. These data can be obtained, free of charge, via
UK; fax +44 1223 336033; or deposit@ccdc.cam.ac.uk).
© 2007 NRC Canada