C6H5), 125.81 (meta-Ph4B), 121.91 (para-Ph4B), 121.60 (para-
C6H5), 84.09 (CNCH2CH2O), 81.75 (Al(NCMe2CH2OC)2B),
68.22 (CNCMe2CH2O), 63.45 (Al(NCMe2CH2OC)2B), 27.87
(Al(NCMe2CH2OC)2B), 27.13 (Al(NCMe2CH2OC)2B), 26.35
(CNCMe2CH2O), -6.43 (AlMe2), -6.92 (AlMe2). 11B NMR (THF-
NMR (benzene-d6, 71 MHz): d -186.7 (Al(NCMe2CH2OC)2B).
IR (KBr, cm-1): 3042 w, 2981 s, 2931 s, 1551 s, 1465 s, 1431 m,
1372 s, 1293 s, 1256 m, 1201 s, 1163 m, 1017 m, 992 s, 828 w, 776 w,
703 s. Anal. Calcd for C19H30BAlN2O2: C, 64.06; H, 8.49; N, 7.86.
Found: C, 63.88; H, 8.49; N, 7.74. mp 150-155 ◦C, dec.
d8, 128 MHz): d -7.51 (BPh4), -12.41 (PhB(OxMe2H)(OxMe2)2). 15
N
NMR (THF-d8, 71 MHz): d -202.8 (HNCMe2CH2OC)B), -176.9
(Al(NCMe2CH2OC)2B). IR (KBr, cm-1): 3361 br m, 3054 s, 2981 s,
2032 s, 1580 s, 1560 s, 1462 s, 1374 s, 1296 m, 1262 m, 1204 s, 1032
m, 969 s, 734 s, 705 sh s, 679 m. Anal. Calcd for C47H56B2AlN3O3:
C, 74.32; H, 7.43; N, 5.53. Found: C, 73.80; H, 7.48; N, 5.10. mp
144-148 ◦C.
[(j2-ToM)AlMe2] (3)
H[ToM] (1.00 g, 2.61 mmol) was dissolved in 50 mL of toluene, and
(AlMe3)2 (0.19 g, 1.32 mmol) was added via syringe. The solution
was stirred for 24 hours to give a pale yellow solution above a small
amount of precipitate. The mixture was filtered and the filtrate was
evaporated under reduced pressure to yield a crude white solid.
Analytically pure [(k -ToM)AlMe2] (0.95 g, 2.17 mmol, 83%) was
2
[Al(j2-ToM)(OiPr)2] (5)
obtained by recrystallization from a toluene/pentane mixture.
A 100 mL Schlenk flask was charged with H[ToM] (0.400 g,
1.04 mmol) and Al(OiPr)3 (0.2134 g, 1.04 mmol). The solids were
dissolved in 50 mL of toluene, and the solution was heated to reflux
under an inert atmosphere for 24 hours. The volatile materials were
removed under reduced pressure leaving the product as a tan solid
(0.34 g, 0.65 mmol, 62%). 1H NMR (benzene-d6, 400 MHz): d 7.97
(d, 2JHH = 7.1 Hz, 2 H, ortho-C6H5), 7.40 (vt, 2JHH = 7.1 Hz, 2 H,
meta-C6H5), 7.22 (t, 2JHH = 7.1 Hz, 1 H, para-C6H5), 4.37 (septet,
2JHH = 5.2 Hz, 2 H, OCHMe2), 3.68 (s, 2 H, CNCMe2CH2O), 3.45
1H NMR (benzene-d6, 400 MHz): d 7.98 (d,3JHH = 7.5 Hz, 2
3
H, ortho-C6H5), 7.43 (vt, JHH = 7.5 Hz, 2 H, meta-C6H5), 7.22
(t,3JHH = 7.5 Hz, 1 H, para-C6H5), 3.69 (s, 2 H, CNCMe2CH2O),
3
3.44 (d, JHH = 8.9 Hz, 2 H, Al(NCMe2CH2OC)2B), 3.21 (d,
3JHH = 8.9 Hz, 2 H, Al(NCMe2CH2OC)2B), 1.32 (s, 6 H,
CNCMe2CH2O), 1.02 (s, 6 H, Al(NCMe2CH2OC)2B), 0.90 (s,
6 H, Al(NCMe2CH2OC)2B), -0.30 (s, 3 H, AlMe), -0.32 (s, 3
1
H, AlMe). 13C{ H} NMR (benzene-d6, 125 MHz): d 196.6 (br,
CNCMe2CH2O), 196.5 (br, CNCMe2CH2O), 146.3 (br, ipso-
C6H5), 134.16 (ortho-C6H5), 127.59 (meta-C6H5), 126.13 (para-
C6H5), 79.83 Al(NCMe2CH2OC)2B), 77.25 (CNCMe2CH2O),
68.04 (CNCMe2CH2O), 65.46 (Al(NCMe2CH2OC)2B), 29.00
2
2
(d, JHH = 8.5 Hz, 2 H, Al(NCMe2CH2OC)2B), 3.25 (d, JHH
=
2
8.5 Hz, 2 H, Al(NCMe2CH2OC)2B), 1.37 (d, JHH = 6.2 Hz, 6
2
H, CHMe2), 1.34 (d, JHH = 6.2 Hz, 6 H, CHMe2), 1.31 (s, 6
H, CNCMe2CH2O), 1.26 (s, 6 H, CNCMe2CH2O), 1.16 (s, 6 H,
(CNCMe2CH2O),
27.07
(Al(NCMe2CH2OC)2B),
26.78
CNCMe2CH2O). 13C{ H} NMR (benzene-d6, 100 MHz): d 145.3
1
(Al(NCMe2CH2OC)2B), -5.88 (s, AlMe), -5.99 (s, AlMe).
11B NMR (benzene-d6, 128 MHz): d -16.5. 15N{ H} NMR
1
(ipso-C6H5), 134.1 (ortho-C6H5), 127.8 (meta-C6H5), 126.1 (para-
C6H5), 80.27 (Al(NCMe2CH2OC)2B), 77.19 (CNCH2CH2O),
67.74 (CNCMe2CH2O), 65.7 (Al(NCMe2CH2OC)2B), 64.02
(CHMe2), 29.15 (CNCMe2CH2O) 28.33 (CHMe2), 27.04
(Al(NCMe2CH2OC)2B), 26.80 (Al(NCMe2CH2OC)2B). 11B NMR
(benzene-d6, 128 MHz): d -16.6. IR (KBr, cm-1): 3070 w, 3048 w,
2966 s, 2930 s, 2887 s, 2628 w, 1593 m, 1562 s sh, 1463 s, 1433 w,
1374 s, 1362 s, 1298 s, 1258 m, 1204 s, 1169 s, 1034 s br, 973 s, 850 w,
741 w, 710 s, 653 w. Anal. Calcd for C27H43BAlN3O5: C, 61.48; H,
8.22; N, 7.97. Found: C, 61.30; H, 8.15; N, 7.56. mp 140-145 ◦C.
(benzene-d6, 71 MHz): -120.2 (CNCMe2CH2O), -184.2
(Al(NCMe2CH2OC)2B). IR (KBr, cm-1): 3053 m, 2968 s,
2930 s, 2889 s, 1626 s, 1565 s, 1462 s, 1433 m, 1373 s, 1360 s,
1294 s, 1252 m, 1200 s, 1160 s, 1100 s, 973 s, 887 m, 677 s. Anal.
Calcd for C23H35BAlN3O3: C, 62.8; H, 8.03; N, 9.56. Found: C,
62.40; H, 8.15; N, 9.26. mp 155-161 ◦C.
[(PhB(OxMe2H)(OxMe2)2)AlMe2][BPh4] (4)
A THF solution of [(k -ToM)AlMe2] (0.150 g, 0.342 mmol)
2
was added to a vial containing [HNMe2Ph][BPh4] (0.158 g,
0.359 mmol). The resulting colorless solution was stirred for
30 min, and then the solvent was removed under reduced pressure.
The crude solid [PhB(OxMe2H)(OxMe2)2AlMe2][BPh4] was washed
with pentane to remove dimethylaniline. Analytically pure off-
white product (0.167 g, 0.220 mmol, 64%) was obtained by
crystallization from a THF/pentane solution at -35 ◦C. 1H
[(j2-ToP)AlMe2] (6)
A solution of H[ToP] (0.700 g, 1.65 mmol) in 50 mL of
toluene was added to a 100 mL Schlenk flask. To this solution
was added (AlMe3)2 (0.125 g, 1.73 mmol). Upon addition
of the (AlMe3)2, methane production was observed as the
solution bubbled vigorously for several minutes. The yellow
solution was stirred for 24 hours under nitrogen. Volatiles
were removed under dynamic vacuum to give the off-white
product (0.503 g, 1.05 mmol, 63.6%). 1H NMR (benzene-d6,
NMR (THF-d8, 400 MHz): d 10.94 (s, 1 H, NH), 7.26 (m, 8
3
H, ortho-Ph4B), 7.25 (m, 2 H, ortho-C6H5), 6.83 (vt, JHH
=
3
7.6 Hz, 8 H, meta-Ph4B), 6.83 (vt, JHH = 7.6 Hz, 2 H, meta-
3
3
2
C6H5), 6.69 (t, JHH = 7.1 Hz, 4 H, para-Ph4B), 6.65 (t, JHH
=
400 MHz): d 8.08 (d, JHH = 7.6 Hz, 2 H, ortho-C6H5), 7.44
2
2
7.1 Hz, 1 H, para-C6H5B), 4.27 (s, 2 H, HNCMe2CH2OC),
(vt, JHH = 7.6 Hz, 2 H, meta-C6H5), 7.24 (t, JHH = 7.6 Hz,
3
4.21 (d, 2 H, JHH = 8.8 Hz, Al(NCMe2CH2OC)2B), 4.09
1 H, para-C6H5), 3.95 (m, 1 H, CNCH(iPr)CH2O), 3.68 (m, 6
3
(d, 2 H, JHH = 8.8 Hz, Al(NCMe2CH2OC)2B), 1.39 (s, 6
H, overlapping OxiPr), 3.52 (m, 1 H, Al(NCH(iPr)CH2OC)2B),
2
H, Al(NCMe2CH2OC)2B), 1.37 (s, 6 H, Al(NCMe2CH2OC)2B),
1.26 (s, 6 H, CNCMe2CH2O), -0.52 (s, 3 H, AlMe), -0.92
3.36 (m, 1 H, Al(NCH(iPr)CH2OC)2B), 2.05 (septet, JHH
=
6.24 Hz, 1 H, Al(NCH(CHMe2)CH2OC)2B), 1.97 (septet,
(s, 3 H, AlMe). 13C{ H} NMR (THF-d8, 125 MHz): d
2JHH = 6.24 Hz, 1 H, Al(NCH(CHMe2)CH2OC)2B), 1.77
1
2
2
190.02 (br, CNCMe2CH2O), 165.20 (q, JB-C = 49.5 Hz, ipso-
(septet, JHH = 6.24 Hz, 1 H, CNCH(CHMe2)CH2O), 1.03
2
Ph4B), 137.19 (ortho-Ph4B), 135.54 (ortho-C6H5), 125.90 (meta-
(d, JHH = 6.93 Hz, 3 H, Al(NCH(CHMe2)CH2OC)2B), 0.93
This journal is
The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 641–653 | 651
©