M.K. Pal et al. / Journal of Organometallic Chemistry 776 (2015) 98e106
105
TZVP basis sets. The calculations have been performed with the
generalized gradient approximation level of theory using Becke's
exchange functional [44] in conjunction with Perdew's correlation
functional (BP86) [45]. The metal-ligand bond lengths and
complexation energy values have been calculated for the com-
plexes. Charge distributions on the metal and donor centers have
also been calculated using the natural population analysis scheme
for the organo-gallium complexes with azo linked salicylaldimine
Schiff bases.
[Me2GaOC6H3(N]NPh) (CH]NCH2e)]2 (6a)
Prepared similar to 5a in 78% yield, mp 100 ꢁC (decomp.). Anal.
Calcd. for C32H34Ga2N6O2: C, 57.12; H, 5.08; N, 12.46%. Found: C,
57.09; H, 5.21; N, 12.42%. IR (y
in cmꢀ1): 1627 (C]N); 1474 (N]N);
588 (GaeC); 544, 533 (GaeO). 1H NMR (dmso-d6)
d: e0.29 (s,
Me2Ga); 3.92 (s, eCH2e, 4H); 6.86 (d, 3JHH ¼ 8.4 Hz, 1H); 7.48e7.54
(m, 6H); 7.78 (d, 3JHH ¼ 7.5 Hz, 4H); 7.94 (d, 3JHH ¼ 8.1 Hz, 2H); 8.01
(s, 2H), 8.71 (s, eCH]Ne, 2H). 13C{1H} NMR (dmso-d6)
d: e6.2 (s,
Me2Ga); 57.0 (eCH2), 117.8 (C-1), 122.1, 122.9, 1283, 129.4, 130.5,
133.3, 142.6, 152.0, 169.1(C-2), 172.7 (s, eCH]Ne).
Synthesis of complexes
[Et2GaOC6H3(N]NPh) (CH]NCH2e)]2 (6b)
[Me2GaOC6H3(N]NPh) (CH]NPh)] (5a)
Prepared similar to 6a in 66% yield, mp 155 ꢁC Calcd. for
To a benzene solution (25 mL) of trimethylgallium etherate
(274 mg, containing 100 mg (0.87 mmol) Me3Ga), was added a
solution of 1a (262 mg, 0.87 mmol) with stirring which continued
for 10 h. The solvent was evaporated under a reduced pressure to
give an orange-red crystalline solid, which was recrystallized from
hexane as an orange-red crystalline solid (254 mg, 73% yield), mp
133 ꢁC, Anal. Calcd. for C21H20GaNO3: C, 63.03; H, 5.04; N, 10.50%.
C36H42Ga2N6O2: C, 59.21; H, 5.80; N, 11.52%. Found: C, 59.32; H,
5.73; N, 11.16%. IR (
y
in cmꢀ1): 1621 (C]N); 1473 (N]N); 560
3
(GaeC); 532 (GaeO). 1H NMR (dmso-d6)
d
: 0.41 (q, JHH ¼ 7.9 Hz
3
eCH2Ga); 1.00 (t, JHH ¼ 7.8 Hz CH3CH2Ga); 3.92 (s, eCH2e, 4H);
6.89 (d, 3JHH ¼ 9.0 Hz, 2H); 7.46e7.57 (m, 6H); 7.79 (d, 3JHH ¼ 7.2 Hz,
4H); 7.96 (d, 3JHH ¼ 9.3 Hz, 2H); 8.01 (s, 2H); 8.80 (s, eCH]Ne, 2H).
13C{1H} NMR (dmso-d6): 3.8 (s, eCH2Ga); 10.0 (s, CH3CH2Ga); 56.4
(NCH2), 118.3 (C-1), 122.5, 123.2, 128.8, 129.2, 129.8, 130.9, 133.8,
142.8, 152.5, 170.3 (C-2), 173.6 (s, eCH]Ne).
Found: C, 62.99; H, 4.88; N, 10.27%. IR (y
in cmꢀ1): 1620 (C]N);
1474 (N]N); 590 (GaeC); 530 (GaeO). 1H NMR (dmso-d6)
d: ꢀ0.29
3
(s, Me2Ga); 6.92 (d, JHH ¼ 9.3 Hz, 1H); 7.44 -7.57 (m, 8H); 7.81(d,
3JHH ¼ 7.8 Hz, 2H); 8.01(d, d, (2.4 Hz) 3JHH ¼ 9.0 Hz, 1H); 8.27 (s, 1H);
[{Me2GaOC6H3(N]NPh) (CH]NCH2CH2}3N] (7a)
8.91 (s, eCH]Ne, 1H). 13C{1H} NMR (dmso-d6)
d
: ꢀ5.8 (s, Me2Ga);
Prepared similar to 5a in 84% yield, mp 89 ꢁC. Anal. Calcd. for
118.4 (C-1), 121.8, 122.1, 123.1, 128.1, 128.3, 129.4, 130.0, 130.5, 135.4,
142.8 (C-5), 146.3 (C-100), 152.0 (C-10), 169.2 (eCH]Ne), 169.5 (C-2).
All the di-and mono-organo gallium complexes were prepared
in a similar manner in 80e90% yield and were recyrstallized from
toluene-hexane or dichloromethane-hexane mixture in 60e85 %
yield.
C
51H57Ga3N10O3: C, 57.39; H, 5.38; N, 13.12%. Found: C, 57.41; H,
5.24; N, 12.95%.IR
in cmꢀ1): 1628 (C]N); 1474 (N]N);
587(GaeC); 532 (GaeO). 1H NMR (dmso-d6)
: e0.32 (s, Me2Ga);
(y
d
3
3
2.92 (t, JHH ¼ 7.0 Hz, eCH2e, 6H); 3.72 (t, JHH ¼ 6.8 Hz, eCH2e,
3
6H); 6.83(d, JHH ¼ 9.0 Hz, 3H); 7.47e7.55 (m, 9H); 7.77 (d,
3JHH ¼ 6.8 Hz, 6H); 7.91(d, 3JHH ¼ 9.0 Hz, 3H); 8.00 (s, 3H); 8.64 (s,
eCH]Ne, 3H). 13C{1H} NMR (dmso-d6)
d: ꢀ5.9 (s, Me2Ga); 53.7
[Et2GaOC6H3(N]NPh) (CH]NPh)] (5b)
(eCH2e), 54.7(eCH2e), 118.3 (C-1), 122.5, 123.2, 129.8, 130.9, 133.5,
143.0152.5, 169.4(C-2), 171.8 (s, eCH]Ne).
Prepared similar to 5a and dissolved in hexane. The hexane
soluble part was dried under reduced pressure to give a paste in
61% yield. IR (
y
in cmꢀ1): 1614 (C]N); 1471 (N]N); 564 (GaeC);
[{Et2GaOC6H3(N]NPh) (CH]NCH2CH2}3N] (7b)
529 (GaeO). 1H NMR (dmso-d6)
d
: 0.38 (q, 3JHH ¼ 7.8 Hz eCH2Ga);
Prepared in 84% yield, mp 70 ꢁC Calcd. for C57H69Ga3N10O3: C,
3
3
0.93 (t, JHH ¼ 7.9 Hz CH3CH2Ga); 6.93 (d, JHH ¼ 9.0 Hz, 1H);
59.46; H, 6.04; N, 12.16%. Found: C, 59.32; H, 5.73; N, 11.16%. IR (y in
3
3
7.44e7.59 (m, 8H), 7.80 (d, JHH ¼ 7.5 Hz, 2H); 7.98 (d,d JHH ¼ 2.4,
cmꢀ1): 1626 (C]N); 1473 (N]N); 560 (GaeC); 530 (GaeO). 1H
9.0 Hz, 1H); 8.25 (s, 1H), 8.98 (s, eCH]Ne, 1H). 13C{1H} NMR
NMR (dmso-d6)
d
: 0.37 (q, JHH ¼ 7.4 Hz eCH2Ga); 1.00 (t,
3
(dmso-d6)
d
: 4.4 (s, eCH2Ga); 10.0 (s, CH3CH2Ga); 118.9 (C-1), 122.0,
3JHH ¼ 6.9 Hz CH3CH2Ga); 2.95 (s, eCH2e, 6H); 3.71 (s, eCH2e, 6H);
6.86 (d, 3JHH ¼ 8.7 Hz, 3H); 7.50e7.53 (br, m, 9H); 7.76e7.79 (br, m
6H); 7.92 (d, 3JHH ¼ 8.1 Hz, 3H); 8.01 (s, 3H); 8.71 (s, eCH]Ne, 3H).
13C{1H} NMR (dmso-d6): 3.7 (s, eCH2Ga); 10.0 (s, CH3CH2Ga); 53.7
(eCH2e), 54.8 (eCH2e), 118.4 (C-1), 122.5, 123.1, 129.8, 130.8, 133.5,
142.9, 152.5, 170.2(C-2), 172.4 (s, eCH]Ne).
122.5, 123.4, 128.6, 129.0, 129.9, 130.5, 130.9, 135.9, 143.1, 146.9,
152.5, 170.0 (s, eCH]Ne), 170.7 (C-2).
[Me2GaOC6H3(N]NPh) (CH]Ntol-4)] (5c)
Prepared in 72% yield, mp 78 ꢁC. Anal. Calcd for C22H22GaN3O: C,
63.80; H, 5.35; N,10.16%. Found: C, 63.17; H, 5.02; N,10.25. %. IR (
y in
cmꢀ1): 1617 (C]N); 1473 (N]N), 591(GaeC); 536 (GaeO). 1H NMR
[C6H5eN]NeC6H3(40-OGaMeO)-30-CH]NeC6H4] (8a)
(dmso-d6)
d
: e0.30 (s, Me2Ga); 2.33 (s, eCH3, 3H); 6.90 (d,
Prepared similar to 5a in 85% yield, mp 255 ꢁC (decomp) Anal.
Calcd. for C20H16GaN3O2: C, 60.04; H, 4.03; N, 10.50%. Found: C,
3JHH ¼ 9.0 Hz, 1H); 7.32 (s, 4H); 7.47e7.56 (m, 3H); 7.80 (d,
3JHH ¼ 7.2 Hz, 2H); 7.98(d, d, (1.2 Hz) 3JHH ¼ 9.0 Hz, 1H); 8.23 (s, 1H);
60.03; H, 4.31; N, 10.44, %. IR (
y
in cmꢀ1): 1614 (C]N); 1483 (N]N),
8.86 (s, eCH]Ne, 1H). 13C{1H} NMR (dmso-d6)
d
: e5.3 (s, Me2Ga);
576(GaeC); 515 (GaeO). 1H NMR (dmso-d6)
d: ꢀ0.53 (s, MeGa);
3
3
21.0 (Me), 118.9 (C-1), 122.0, 122.5, 123.4, 128.8, 129.8, 130.8, 130.9,
135.7, 138.2, 143.2, 144.2, 152.5, 168.8 (s, eCH]Ne), 169.8(C-2).
6.60 (t, JHH ¼ 7.02 Hz, 1H); 6.70 (d, JHH ¼ 7.8 Hz, 1H); 6.87(d,
3
3JHH ¼ 9.0 Hz, 1H); 7.08 (t, JHH ¼ 7.5 Hz, 1H); 7.48e7.57 (m, 3H);
7.62 (d, 7.80 3JHH ¼ 7.8 Hz, 1H); 7.80 (d, 3JHH ¼ 7.5 Hz, 2H); 7.90 (d,
[Et2GaOC6H3(N]NPh) (CH]Ntol-4)] (5d)
3JHH ¼ 8.7 Hz, 1H); 8.13 (s, 1H); 9.11 (s, eCH]Ne, 1H). 13C{1H} NMR
Prepared in 63% yield as a paste. IR (
y
in cmꢀ1): 1616 (C]N);
(dmso-d6)
d
: ꢀ6.7 (s, MeGa); 115.7, 115.8, 117.8, 119.7 (C-1), 122.5,
1468 (N]N); 562 (GaeC); 535 (GaeO). 1H NMR (dmso-d6)
d: 0.37
123.5, 127.4, 129.8, 130.5, 130.7, 132.2, 132.3, 143.0, 152.6, 158.0 (s,
(q, 3JHH ¼ 8.0 Hz eCH2Ga); 0.93 (t, 3JHH ¼ 8.0 Hz CH3CH2Ga); 2.36 (s,
eCH]Ne), 159.2 (C-200), 170.6 (C-2).
3
eMe); 6.92 (d, JHH ¼ 9.3 Hz, 1H); 7.35 (s, 4H); 7.49e7.58 (m, 3H);
3
7.80 (d, JHH ¼ 7.2 Hz, 2H); 7.98 (d,3JHH ¼ 2.4, 9.0 Hz, 1H); 8.23 (s,
[C6H5eN]NeC6H3(40-OGaEtO)-30-CH]NeC6H4] (8b)
1H), 8.96 (s, eCH]Ne, 1H). 13C{1H} NMR (dmso-d6)
d: 4.4 (s,
Prepared similar to 5a and washed with hexane to give 86%
eCH2Ga); 10.0 (s, CH3CH2Ga); 21.0 (Me), 118.9 (C-1), 121.7, 122.5,
123.3, 128.9, 129.9, 130.9, 135.7, 138.3, 143.1, 144.5, 152.5, 169.2 (s,
eCH]Ne), 170.6 (C-2).
yield, mp 265 ꢁC (decomp.). Calcd. for C21H18GaN3O2: C, 60.91; H,
4.38; N, 10.14%. Found: C, 60.66; H, 4.25; N, 10.08%. IR (
1615 (C]N); 1473 (N]N), 557 (GaeC); 528 (GaeO). 1H NMR
y
in cmꢀ1):