D.L. Davies et al. / Journal of Organometallic Chemistry 693 (2008) 965–980
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mixture was stirred under N2 with exclusion of light for 2 h.
This suspension was filtered through celite to remove AgCl.
The resulting solution was evaporated to dryness affording
an oil. Trituration with Et2O gave 9a as a brown solid.
(121 mg, 82%): Anal. Calc. for C29H27O4NPSF3Pd: C,
51.22; H, 4.00; N, 2.06. Found: C, 52.06; H, 4.46; N,
H5), 7.01 (t, 1H, J 7.5, H4), 7.37 (dd, 1H, J 7.5, 1.5, H3),
7.55 (m, 9H, (Hm, Hp) PPh3), 7.68 (m, 6H, (Ho) PPh3),
8.23 (d, 1H, JPH 8, HC@N); 13C NMR: d 28.36 (–CH2–),
56.24 (CH2), 62.43 (OMe), 73.71 (CH2), 126.12, 130.07,
130.799 (C3,C4, C5), 138.32 (d, J 10, C6), 128.15 ((Ci)
PPh3), 129.43 (d, J 11, Cm, PPh3), 132.28 (Cp (PPh3)),
135.12 (d, J 13, Co, PPh3), 147.60 (C2), 175.62 (HC@N);
31P–{1H} NMR: 39.85. MS (FAB) m/z 544 [MꢀSbF3]+.
1
1.99%. H NMR: d 3.34 (s, 3H, OMe), 3.78 (t, 2H, J 4.5,
CH2O), 4.02 (m, 2H, NCH2), 6.35 (m, 1H, H6), 6.56 (dt,
1H, J 7.5, 1, H5), 6.96 (t, 1H, J 7.5, H4), 7.30 (dd, 1H, J
7.5, 2, H3), 7.47 (m, 9H, (Hm, Hp) PPh3), 7.71 ([m, 6H,
(Ho) PPh3), 8.17 (d, 1H, JPH 7.5, HC@N); 13C NMR: d
58.28 (NCH2), 59.50 (OMe), 72.19 (OCH2), 125.47,
129.51 (3C, 5C), 130.59 (d, J 5.5, C3), 138.34 (d, J 12,
C6), 128.50 ((Ci) PPh3), 129.08 (d, J 12, (Hm)PPh3),
131.77 (d, J 2.5, (Cp)PPh3), 135.27 (d, J 12, (Co) PPh3),
148.04 (C2), 150.13 (C1), 176.39 (HC@N); 31P–{1H}
NMR: 39.94. MS (FAB) m/z 530 [MꢀOTf]+. IR:
IR: t(C@N) 1633 cmꢀ1
.
3.19. Preparation of [Pd{C6H4-2-C(H)@NCH2CH2CH2-
OH-K-C1,N,O}(PPh3)][OTf] (7d, X = OTf)
To a suspension of 5d (35 mg, 0.062 mmol) in acetone
(15 ml), AgOTf (16 mg, 0.062 mmol) was added. The mix-
ture was stirred under N2 with exclusion of light for 2 h.
This suspension was filtered over celite to remove AgCl.
The resulting solution was evaporated to dryness affording
a oil product. Treatment with Et2O gave 7d (X = OTf) as a
beige precipitate. (36 mg, 82%): Anal. Calc. for
C29H27O4NPSF3Pd: C, 51.22; H, 4.00; N, 2.06. Found:
t(C@N) 1638 cmꢀ1
.
3.17. Preparation of [Pd{C6H4-2-C(H)@NCH2CH2O-
CH3-K-C1,N,O}(PPh3)](SbF6) (7a, X = SbF6)
1
C, 51.06; H, 3.96; N, 1.98%. H NMR: d 1.97 (q, 2H, J
To a suspension of 5a (120 mg, 0.21 mmol) in dry
CH2Cl2 (15 ml), AgSbF6 (73 mg, 0.21 mmol) was added.
The mixture was stirred under N2 with exclusion of light
for 2 h. and then filtered through celite to remove AgCl.
The resulting solution was evaporated to dryness affording
an oily product. Treatment with Et2O gave 7a (X = SbF6)
as a pale white solid. (151 mg, 91%): Anal. Calc. for
C28H27ONPSbF6Pd: C, 43.87; H, 3.55; N, 1.83. Found:
C, 43.69; H, 3.39; N, 1.83%. 1H NMR: d 3.19 (s, 3H,
OMe), 3.84 (m, 2H, CH2O), 3.94 (m, 2H, NCH2), 6.32
(dd, 1H, J 7.5, JPH 4.5, H6), 6.59 (dt, 1H, J 7.5, 1.5, H5),
6.99 (t, 1H, J 7.5, H4), 7.37 (dd, 1H, J 7.5, 1.5, H3), 7.50
(m, 9H, (Hm, Hp) PPh3), 7.70 (m, 6H, (Ho) PPh3), 8.22
(d, 1H, JPH 6.5, HC@N); 13C NMR: d 57.42 (NCH2),
60.04 (OMe), 73.85 (OCH2), 125.91, 130.16 (C3, C4, C5),
138.34 (d, J 12, C6), 128.18 ((Ci) PPh3), 129.36 (d, J 12,
(Hm)PPh3), 132.18(d, J 2.5, (Cp) PPh3), 135.10 (d, J 12,
(Co)PPh3), 148.79 (C2), 151.00 (C1), 177.04 (HC@N); 31P-
{1H} NMR: 39.94. MS (FAB) m/z 530 [MꢀSbF6]+. IR:
5.5, –CH2–), 3.69 (m, 2H, CH2O), 3.80 (m, 2H, NCH2),
5.72 (t, 1H, J 4.5, OH), 6.29 (dd, 1H, J 7.5, JPH 5.5, H6),
6.51 (dt, 1H, J 7.5, 1.5, H5), 6.88 (dt, 1H, J 7.5, 1, H4),
7.23 (dd, 1H, J 7.5, 1.5, H3), 7.35 (m, 9H, (Hm, Hp)
PPh3), 7.60 (m, 6H, (Ho) PPh3), 8.09 (d, 1H, JPH 8,
HC@N); 13C NMR: d 30.72 (–CH2–), 56.30 (CH2), 63.52
(CH2), 125.39, 129.27 (4C,5C), 130.91 (d, J 5.5, C3),
138.53 (d, J 11, C6), 127.82 ((Ci) PPh3), 128.90 (d, J 11,
(Cm) PPh3), 131.74 (d, J 2.5, (Cp) PPh3), 135.35 (d, J 12,
Co) (PPh3), 147.15 (C2), 150.32 (C1), 174.45 (HC@N);
31P–{1H} NMR: 39.81. MS (FAB) m/z 530 [MꢀOTf]+.
IR: t(C@N) 1637 cmꢀ1
.
3.20. Preparation of [Pd{C6H2-4,5-(OCH3)2-2-C(H)@
NCH2CH2CH2OH-K-C1,N,O} (PPh3)][OTf] (7e,
X = OTf)
To a suspension of 5e (70 mg, 0.11 mmol) in acetone
(15 ml), AgOTf (29 mg, 0.11 mmol) was added. The sus-
pension was stirred under N2 with exclusion of light for
2 h, and then filtered over celite to remove AgCl. The fil-
trate was evaporated to dryness giving an oil product.
Treatment with Et2O gave 7e (X = OTf) as a beige solid.
(72 mg, 83%): Anal. Calc. for C31H31O6NPSF3Pd ꢂ (0.5
H2O): C, 49.71; H, 4.31; N, 1.87. Found: C, 48.76; H,
t(C@N) 1626 cmꢀ1
.
3.18. Preparation of [Pd{C6H4-2-C(H)@NCH2CH2CH2O-
CH3-K-C1,N,O}(PPh3)](SbF6) (7b, X = SbF6)
To a suspension of 5b (85 mg, 0.15 mmol) in acetone
(15 ml), AgSbF6 (51 mg, 0.15 mmol) was added. The sus-
pension was stirred under N2 with exclusion of light for
2 h then filtered through celite to remove AgCl. The filtrate
was evaporated to dryness affording a brown oil. Treat-
ment with Et2O gave 7b (X = SbF6) as a pale white solid.
(98 mg, 84%): Anal. Calc. for C29H29ONPSbF6Pd: C,
44.62; H, 3.74; N, 1.79. Found: C, 44.55; H, 3.63; N,
1.84%.1H NMR: d 2.15 (q, 2H, J 5.5, –CH2–), 2.95 (s,
3H, OMe), 3.62 (t, 2H, J 5.5, CH2O), 3.92 (q, 2H, J 5,
NCH2), 6.29 (dd, 1H, J 7.5, 6, H6), 6.58 (t, 1H, J 7.5,
1
3.88; N, 1.64%. H NMR: d 2.00 (m 2H, –CH2–), 2.86 (s,
3H, OCH3), 3.69 (m, 2H, CH2O), 3.79 (s, 3H, OCH3),
3.96 (m, 2H, NCH2), 5.75 (br, 1H, OH), 5.86 (d, 1H, J
5.5, H6), 6.91 (s, 1H, H3), 7.49 (m, 9H, (Hm, Hp) PPh3),
7.66 (m, 6H, (Ho) PPh3), 8.07 (d, 1H, JPH 8, HC@N);
13C NMR: d 30.83 (–CH2–), 55.43, 56.15 (2 ꢁ OCH3),
55.98 (CH2), 63.68 (CH2), 111.79 (C3), 121.62 (d, J 12,
C6), 127.84 ((Ci) PPh3), 128.51, 138.68 (C4, C5), 129.00
(d, J 11, Cm (PPh3), 131.88 (d, (Cp) PPh3), 135.35 (d, J
12.6, (Co)PPh3), 146.51 (C1), 173.75 (HC@N); 31P–{1H)