Homopolymers and Copolymers Containing closo-[B12H12]2À Boron Cages
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MeS), 1.53 ppm (brs, 10H, BH); GPC (DMF, 10 mm LiCl, 708C): MN =
4260 gmolÀ1, PDI=2.69.
the formation of a white solid. The white solid was filtered and washed
with toluene (11). 1H NMR (250 MHz, [D6]DMSO, 258C, TMS): d=4.71
(brs, 1H, OH), 1.78 (brs, 2H, CH2O), 3.47 (brs, 2H, CH2C=O), 2.58
(brs, MeS +Me2S), 1.6–2.1 (brs, 2H, CH2), 0.66, 0.83 ppm (brs, 3H,
CH3).
Poly(tetrabutylammonium)(undecahydrododecaborane-1-methylsulfido-
4’-methylstyrene (6a): AIBN (0.0002 g) was added to a solution of 3
(0.018 g, 0.033 mmol) in 2-methyl-THF (1 mL), and the solution was
heated slowly to 758C. It was heated for 6 h at 758C. An oily substance
stuck to the wall of the glassware. The 2-methyl-THF was decanted and
the oily substance was washed with more 2-methylTHF. The oily sub-
stance was dried at 808C and a white solid was isolated (6a). 1H NMR
(250 MHz, CD3CN, 258C): d=6.7–7.2 (brs, 2H, CHAr), 6.15–6.7 (brs, 2H,
CHAr), 3.95–4.4.45 (brs, 1H, CH2S), 3.5–3.9 (brs, 1H, CH2S), 3.03 (m,
8H, CH2N), 2–2.25 (br m, 3H, MeS), 1.51 (m, 8H, CH2), 1.25 (q, 8H,
CH2), 0.96 ppm (t, 12H, CH3); 11B NMR (80 MHz, CDCl3, 258C): d=
À14.2 (d), À15.9 ppm (d); GPC (DMF, 10 mm LiCl, 708C): MN =3.98
x104 gmolÀ1, PDI=15.54.
Poly(7-(dimethylsulfido)decahydrododecaborane-1-methylsulfidoethyl-
methacrylate-co-hydroxyethylmethylmethacrylate) (12): Monomer
1
(0.05 g, 0.134 mmol) and AIBN (0.003 g) were added to HEMA (0.25 g,
1.92 mmol). The solution was heated at 808C for 18 h to give a white
polyACTHNUTRGNEmNUG er (insoluble polymer) (12). IR (KBr): n˜ =3448.6 (br, OH), 2950.6
(C–H), 2524.4 (B–H), 1719.1 cmÀ1 (C=O).
Poly(7-(dimethylsulfido)decahydrododecaborane-1-methylsulfidoethyl-
methacrylate-co-hydroxyethylmethylmethacrylate) (13): The synthetic
procedure for 12 was used for the synthesis of 13 (see Supporting Infor-
mation). 1H NMR (250 MHz, [D7]DMF, 258C, TMS): d=4.96 (brs, 1H,
OH), 4.45 (brs, 2/15H, CH2O), 4.07 (brs, 2H, CH2O), 3.77 (brs, 2H,
CH2C=O), 2.77 (brs, 3H/15, MeS), 2.68 (brs, 6H/15, Me2S), 2.95–2.2,
1.55–1.7, 1.2–1.35 (br m, CH2), 0.95, 1.06 ppm (brs, 3H, CH3); 11B NMR
(80 MHz, [D7]DMF, 258C, BF3·OEt2): d=À16 ppm (brs); IR (KBr): n˜ =
3437 (OH), 2950 (C–H, aliphatic), 2526 (B–H), 1725.8 cmÀ1 (C=O).
Poly(tetrabutylammonium)(undecahydrododecaborane-1-methylsulfido-
4’-methylstyrene (6b): The synthetic procedure of 4b was used for the
ACTHNUTRGNEUNG
synthesis of 6b (see Supporting Information). 1H{11B} NMR (250 MHz,
[D6]DMSO, 258C): d=7.48 (brs, 2H, CHAr), 6.46 (brs, 2H, CHAr), 4.21
(brs, 1H, CH2S), 3.82 (brs, 1H, CH2S), 3.17 (brs, 8H, CH2N), 2.22 (br m,
3H, MeS), 1.58 (brs, 8H, CH2), 1.32 (brs, 8H, CH2), 1.16 (s, 11H, BH),
0.95 ppm (brs, 12H, CH3); GPC (10 mm LiCl in DMF, 708C) MN =
9600 gmolÀ1, PDI=2.45.
Poly(7-(dimethylsulfido)decahydrododecaborane-methylsulfidoethylme-
thacrylate-co-hydroxyethylmethacrylate) (14): The synthetic procedure
for 12 was used for the synthesis of 14 (see Supporting Information).
1H NMR (250 MHz, [D7]DMF, 258C, TMS): d=4.86 (brs, 1H, OH, 4.46
(brs, 2H/15, CH2O), 4.18 (brs, 2H, CH2O), 3.74 (brs, 2H, CH2C=O),
2.785 (brs, 3H/15, MeS), 2.67 (brs, 6H/15, Me2S), 2.456, 1.959, 1.752 ppm
(brs, 2H, CH2); 11B NMR (80 MHz, [D7]DMF, 258C): d=À15.6 ppm
(br); IR (KBr): n˜ =3435 (OH), 2954 (C–H) aliphatic), 2523 (B–H)),
1735 cmÀ1 (C=O).
Poly(7-dimethylsulfido)decahydrodecaborane-1-methylsulfidoethylmetha-
crylate-co-methylmethaylacrylate) (7): Monomer 1 (0.0762 g, 0.21 m mol)
was dissolved in MMA (0.38 g, 3.8 mmol) and AIBN (0.005 g) was
added. The solution was heated at 1008C for 17 h to form a transparent
solid (7). 1H NMR (250 MHz, CDCl3, 258C): d=4.34 (brs, 2H/18,
CH2O), 3.62 (brs, 3H, CH3O), 3.15 (brs, 1H/18, CH2S), 3.4 (brs„ 1H/18,
CH2S), 2.65 (brs, 3H/18, MeS), 2.57 (brs, 6H/17.5, Me2S), 1.6–2.1 (br,
2H, CH2), 0.87, 1.043 ppm (brs, 3H, CH3); 11B NMR (80 MHz, CDCl3,
258C): d=À9.8 (br), À16 ppm (br); IR (KBr): n˜ =2997.9, 2952.16 ((C–
H)aliphatic), 2523.2 (B–H), 1734.30 cmÀ1 (C=O); GPC (THF, 408C):
MN =45000 gmolÀ1, PDI=1.98.
Poly(7-(dimethylsulfido)decahydrododecaborane-1-methylsulfidoethyl-
methacrylate-co-hydroxyethylmethacrylate) (15): The synthetic proce-
dure for 11 was used for the synthesis of 15 (see Supporting Informa-
tion). 1H NMR (250 MHz, [D6]DMSO, 258C, TMS): d=4.75 (brs, 1H,
OH), 4.15–4.55 (brs, 2H/15, CH2O), 3.99 (brs, 2H, CH2O), 2.66 (brs,
MeS + Me2S), 1.78, 1.57 ppm (brs, 2H, CH2).
Poly(7-(dimethylsulfido)decahydrododecaborane-1-methylsulfidoethyl-
methacrylate-co-methylmethacrylate) (8): Monomer
1
(0.042 g,
Poly(7-(dimethylsulfido)decahydrododecaborane-1-methylsulfidoethyl-
methacrylate-co-acrylamide) (16): Monomer 1 (0.035 g, 0.096 mmol), ac-
rylamide (0.175 g, 2.46 mmol), and AIBN (0.002 g) were added to aceto-
nitrile (1 mL). The solution was heated at 708C for 4 h. The white solid
formed was filtered and washed with acetonitrile (16). 1H NMR
(250 MHz, [D6]DMSO, 258C, TMS): d=7.07, 6.69 (brs, 2H, NH2), 4.15
(brs, 2H/15, CH2O), 2.51 (brs, 6H/15, Me2S), 1.97, 1.36 ppm (brs, 2H,
CH2); 11B NMR (80 MHz, [D6]DMSO, 258C): d=À16.9 ppm (br); IR
(KBr): n˜ =3342, 3196 (N–H), 2934 (C–H, aliphatic), 2523 (B–H),
1663 cmÀ1 (br, C=O).
0.112 mmol) and MMA (0.025 g, 0.25 mmol) were dissolved in toluene
(1 mL) and the solution was heated at 808C in the presence of AIBN
(0.0008 g) for 16 h. The white solid that precipitated was washed with tol-
1
uene and dried under vacuum (8). H NMR (250 MHz, [D7]DMF, 258C):
d=4.39 (brs, 2H, CH2O, 3.55 (brs, 3H, CH3O), 3.35 (brs, 2H, CH2S),
2.70 (brs, 3H, MeS), 2.65 (brs, 6H, Me2S), 1.7–2.2 (br, 4H, CH2), 0.78,
0.94 ppm (brs, 6H, CH3); 11B NMR (80 MHz, [D7]DMF, 258C): d=À9.3
(sh), À14.9 ppm (brs); IR (KBr): n˜ =2994, 2949 (CH2, CH3), 2519.8 (s,
B–H), 1731 cmÀ1 (s, C=O); GPC (DMF, 10 mm LiCl, 708C): MN =8.53ꢂ
104 gmolÀ1, PDI=4.06.
Poly(7-(dimethylsulfido)decahydrododecaborane-1-methylsulfidoethyl-
Poly(7-(dimethylsulfido)decahydrododecaborane-1-methylsulfidoethyl-
methacrylate-co-styrene) (9): Monomer 1 (0.05 g, 0.14 mmol) was added
to styrene (0.25 g, 2.4 mmol) followed by AIBN (0.003 g). The solution
was heated at 1008C for 16 h to give a transparent solid (9). 1H NMR
(250 MHz, CDCl3, 258C): d=6.6–7.1 (brs, CHAr), 6.15–6.6 (br, CHAr),
2.40 (brs, Me2S +MeS), 1.5–1.9 (brs, CH), 1.1–1.5 ppm (brs, CH2);
11B NMR (80 MHz, CDCl3, 258C): d=À9.8 (sh), À15.3 ppm (brs); IR
(KBr): n˜ =3082, 3059, 3025 cmÀ1 (C–H, aromatic), 2921, 2849 (CH2, CH,
aliphatic), 2517.3 (B–H), 1734.1 cmÀ1 (C=O), 1600.77 cmÀ1 (C=C, aromat-
ic); GPC (THF, DMF, 408C): MN =12000 gmolÀ1, PDI=2.72.
methacrylate-co-hydroxyethylmethylmethacrylate)
(17):
HEMA
(0.0306 g, 0.24 mmol) and 1 (0.0305 g, 0.084 mmol) were dissolved in tolu-
ene (0.5 mL) to form a clear solution. AIBN (0.0007 g) was added and
the reaction mixture was heated at 1008C for 2 h. A white solid stuck to
the surface of the reaction glass. The toluene was decanted, and the
white solid was washed with more toluene and dichloromethane and then
dried. The white solid was isolated by scraping it from the glass (17).
1H NMR (250 MHz, [D6]DMSO, 258C, TMS): d=4.83 (brs, 1H, OH),
4.15–4.5 (brs, 2H/2, CH2O), 3.91 (brs, 2H, CH2O), 3.59 (brs, 2H, CH2O),
3.27 (brs, 2H/2, CH2S), 2.62 (brs, 3H/2, MeS), 2.52 (brs, 6H/2, Me2S),
1.65–2.1 (brs, 3H, CH2a), 0.78, 0.955 ppm (brs, 4.5H, CH3); 11B NMR
(80 MHz, [D6]DMSO, 258C): d=À15.2 ppm (brs); IR (KBr): n˜ =3429
(brs, OH), 2938 (CH2, CH3), 2520 (B–H), 1726 cmÀ1 (C=O); GPC (DMF,
10 mm LiCl, 708C): MN =19050 gmolÀ1, PDI=2.52.
Poly(7-(dimethylsulfido)decahydrododecaborane-1-methylsulfidoethyl-
methacrylate-co-styrene) (10): The synthetic procedure for 9 was used
1
for the synthesis of 10 (see Supporting Information). H NMR (250 MHz,
[D6]DMSO, 258C, TMS): d=6.8–7.2 (brs, CHAr), 6.3–6.7 (br, CHAr), 2.55
(brs, Me2S
+ MeS), 1.7–1.2 (brs, CH), 1.1–1.65 ppm (brs, CH2); IR
Poly(7-(dimethylsulfido)decahydrododecaborane-1-methylsulfidoethyl-
methacrylate-co-hydroxyethylmethacrylate) (18): The synthetic proce-
dure for 17 was used for the synthesis of 18 (see Supporting Informa-
(KBr): n˜ =3082, 3059, 3025 (C–H, aromatic), 2925, 2849 (CH2, CH)),
2517.7 (B–H), 1729 (C=O), 1600 cmÀ1 (C=C, aromatic); GPC (DMF,
10 mm LiCl, 708C): MN =1.65ꢂ105 gmolÀ1, PDI=4.38.
1
tion). H NMR (250 MHz, [D6]DMSO, 258C, TMS): d=4.82 (brs, 0.18H,
Poly(7-(dimethylsulfido)decahydrododecaborane-1-methylsulfidoethyl-
methacrylate-co-hydroxyethylmethylmethacrylate) (11): HEMA (0.125 g,
0.96 mmol), 1 (0.025 g, 0.069 mmol), and AIBN (0.002 g) were added to
toluene (0.5 mL) and the solution was heated at 808C for 6 h resulting in
OH), 4.1–4.5 (brs, 2H/3, CH2O), 4.00 (brs, 2H, CH2O), 3.59 (brs, 2H,
CH2O), 3.25 (brs, 2H/3, CH2S), 2.59 (brs, 3H/3, MeS), 2.52 (brs, 6H/3,
Me2S), 1.65–2.1 (brs, 2.67H, CH2 aliphatic), 0.78, 0.955 ppm (brs, 1H,
CH3); IR (KBr): n˜ =3448 (brs, OH), 2952 (CH2, CH3), 2520 (B–H),
Chem. Eur. J. 2009, 15, 2190 – 2199
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