Organometallics
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clear solution. The organic phase was separated, dried over MgSO4,
and evaporated. The crude product was purified by column
chromatography over silica gel using dichloromethane−-methanol at
a 20:1 ratio as the eluent. The first two minor bands were discarded,
and the third major band was collected and evaporated to afford 1b as
an orange solid (0.159 g, 64%).
1H NMR (DMSO-d6): δ 3.07−3.14 (m, 3 H, CH2 and allyl CH2),
3.14−3.21 (m, 3 H, CH2 and allyl CH2), 3.82 (br s, 1 H, allyl CH2),
4.35 (virtual d, J′ = 1.5 Hz, 2 H, fc), 4.39 (vt, J′ = 1.8 Hz, 2 H, fc), 4.47
(s, 2 H, fc), 4.64 (br s, 1 H, allyl CH2), 4.81 (vt, J′ = 1.9 Hz, 2 H, fc),
5.53 (s, 2 H, NH2), 5.84 (qi, J = 10 Hz, 1 H, allyl CH), 6.04 (t, 3JHH
=
5.4 Hz, 1 H, NH), 7.43−7.52 (m, 10 H, PPh2), 7.92 (t, 3JHH = 5.4 Hz,
1 H, NH). 31P{1H} NMR (DMSO-d6): δ 16.8 (s). IR (Nujol, cm−1): ν
3437 m, 3378 m, 3188 br m, 3078 w, 1712 w, 1673 s, 1622 s, 1557 s,
1514 s, 1440 w, 1433 m, 1306 s, 1237 m, 1194 m, 1167 m, 1153 m,
1098 m, 1071 w, 1060 w, 1034 m, 1013 w, 972 w, 928 w, 843 m, 814
m, 767 m, 757 m, 746 m, 702 m, 632 m, 585 m, 541 m, 524 m, 510 w,
486 s, 471 m, 444 w, 430 m, 412 m. ESI+ MS: m/z 646 ([M − Cl]+).
Anal. Calcd for C29H31ClFeN3O2PPd (682.24): C, 51.05; H, 4.58; N,
6.16. Found: C, 50.83; H, 4.40; N, 5.83.
1H NMR (DMSO): δ 3.08−3.14 (m, 2 H, CH2), 3.14−3.21 (m, 2
H, CH2), 4.06 (vq, J′ = 1.8 Hz, 2 H, fc), 4.12 (vt, J′ = 1.9 Hz, 2 H, fc),
4.38 (vt, J′ = 1.8 Hz, 2 H, fc), 4.68 (vt, J′ = 1.9 Hz, 2 H, fc), 5.54 (s, 2
H, NH2), 6.06 (t, 3JHH = 5.4 Hz, 1 H, NH), 7.27−7.34 (m, 4 H, PPh2),
7.34−7.40 (m, 6 H, PPh2), 7.89 (t, 3JHH = 5.2 Hz, 1 H, NH). 13C{1H}
NMR (DMSO): δ 68.79 (s, 2 C, CH fc), 71.10 (s, 2 C, CH fc), 72.90
(d, JPC = 4 Hz, 2 C, CH fc), 73.42 (d, JPC = 15 Hz, 2 C, CH fc), 76.51
(d, 1JPC = 9 Hz, 1 C, C−P fc), 77.30 (s, 1 C, C−CO fc), 128.20 (d, 3JPC
= 7 Hz, 4 C, CHmeta PPh2), 128.53 (s, 2 C, CHpara PPh2), 132.91 (d,
Complex 5c. [PdCl(η3-C3H5)]2 (9.1 mg, 0.025 mmol) and 1c (26.4
mg, 0.050 mmol) were reacted in 1.5 mL of dichloromethane, as
described above. Evaporation afforded 5c as an orange solid in a
virtually quantitative yield.
1
2JPC = 19 Hz, 4 C, CHortho PPh2), 138.30 (d, JPC = 10 Hz, 2 C, Cipso
PPh2), 159.03 (s, 1 C, NHC(O)NH2), 168.33 (s, 1 C, fcC(O)NH).
31P{1H} NMR (DMSO): δ −18.1 (s). IR (Nujol, cm−1): ν 3391 m,
3
1H NMR (CDCl3): δ 1.13 (t, JHH = 7.2 Hz, 3 H, CH2CH3), 2.67
3350 m, 3246 br m, 3087 w, 1676 m, 1641 m, 1606 s, 1563 s, 1432 m,
1344 w, 1313 m, 1287 w, 1251 w, 1224 w, 1191 w, 1163 m, 1129 w,
1087 w, 1066 w, 1026 m, 969 w, 932 w, 833 m, 814 w, 775 w, 743 s,
694 s, 634 m, 596 m, 557 w, 511 m, 492 s, 449 m. ESI+ MS: m/z 522
([M + Na]+). Anal. Calcd for C26H26FeN3O2P (499.32): C, 62.54; H,
5.25; N, 8.42. Found: C, 62.57; H, 5.12; N, 8.25.
3
(d, JHH = 12.0 Hz, 1 H, allyl CH2), 2.74 (d, JHH = 5.4 Hz, 1 H, allyl
3
CH2), 3.23 (dq, JHH = 5.6, 7.2 Hz, 2 H, CH2CH3), 3.38−3.58 (m, 4
H, CH2), 3.65 (s, 1 H, fc), 3.82 (s, 1 H, fc), 3.88 (dd, J = 9.8, 13.9 Hz,
1 H, allyl CH2), 4.27 (s, 2 H, fc), 4.58 (s, 1 H, fc), 4.60 (s, 1 H, fc),
4.79−4.86 (m, 2 H, allyl CH2 and NH), 5.02 (s, 1 H, fc), 5.18 (s, 1 H,
fc), 5.64−5.75 (m, 2 H, allyl CH and NH), 7.35−7.60 (m, 9 H, PPh2
and NH), 7.72−7.80 (m, 2 H, PPh2). 31P{1H} NMR (CDCl3): δ 11.9
(s). IR (Nujol, cm−1): ν 3295 br m, 1634 s, 1538 s, 1435 m, 1303 s,
1184 m, 1168 m, 1097 m, 1060 w, 1027 m, 998 w, 964 w, 916 w, 840
m, 749 m, 696 s, 629 w, 542 w, 519 m, 493 m, 468 m, 412 w. ESI+
MS: m/z 674 ([M − Cl]+). Anal. Calcd for C31H35ClFeN3O2PPd·
0.33CH2Cl2 (738.32): C, 50.96; H, 4.87; N, 5.69. Found: C, 50.81; H,
4.88; N, 5.31.
Synthesis of (η3-Allyl)palladium Complexes 5a−g: General
Procedure. A suspension of ligand 1 in dichloromethane was added
to a stoichiometric amount of bis(μ-chloro)bis(η3-allyl)dipalladium
(solid). The resulting mixture was stirred for 30 min, whereupon the
solid educt dissolved to yield an orange solution. This solution was
then filtered through a poly(tetrafluoroethylene) (PTFE) syringe filter
(pore size 0.45 μm) and evaporated to dryness.
Complex 5a. Compound 1a (0.249 g, 0.50 mmol) and [PdCl(η3-
C3H5)]2 (0.0915 g, 0.25 mmol) were reacted in 10 mL of
dichloromethane. The reaction solution was not evaporated but
instead layered with diethyl ether and hexanes. Subsequent
crystallization by liquid-phase diffusion over several days afforded 5a
as an orange crystalline solid (0.268 g, 79%).
Complex 5d. [PdCl(η3-C3H5)]2 (18.3 mg, 0.050 mmol) and 1d
(52.7 mg, 0.10 mmol) were reacted in 2 mL of dichloromethane, as
described above. Rather than being evaporated, the filtered reaction
mixture was layered with diethyl ether and hexanes and allowed to
crystallize by liquid-phase diffusion over several days. The separated
solid was filtered off and dried under vacuum to give 5d (42.2 mg,
59%) as orange microcrystals.
1H NMR (CDCl3): δ 2.04 (s, 3 H, CH3CO), 2.63 (d, JHH = 12.3
Hz, 1 H, allyl CH2), 2.82 (d, JHH = 5.7 Hz, 1 H, allyl CH2), 3.46 (qi,
3JHH ≈ 5.0 Hz, 2 H, CH2), 3.55 (q, 3JHH ≈ 5.5 Hz, 2 H, CH2), 3.58 (br
1H NMR (DMSO): δ 2.77 (s, 6 H, N(CH3)2), 3.12−3.18 (m, 2 H,
CH2), 3.18−3.25 (m, 2 H, CH2), 3.82 (br s, 2 H, allyl CH2), 4.34 (m,
2 H, fc), 4.40 (vt, J′ = 1.8 Hz, 2 H, fc), 4.45 (vt, J′ = 1.5 Hz, 2 H, fc),
4.64 (br s, 2 H, allyl CH2), 4.82 (vt, J′ = 1.9 Hz, 2 H, fc), 5.94 (qi, J =
10.0 Hz, 1 H, allyl CH), 6.41 (t, 3JHH = 5.2 Hz, 1 H, NH), 7.43−7.52
s, 1 H, fc), 3.80 (br s, 1 H, fc), 3.87 (dd, J = 9.7, 13.8 Hz, 1 H, allyl
CH2), 4.23 (br s, 1 H, fc), 4.26 (br s, 1 H, fc), 4.58 (br s, 2 H, fc), 4.81
(dt, J = 1.2, 7.6 Hz, 1 H, allyl CH2), 5.04 (br s, 1 H, fc), 5.21 (br s, 1 H,
fc), 5.69 (ddd, J = 7.6, 13.8, 19.0 Hz, 1 H, allyl CH), 7.01 (br s, 1 H,
NH), 7.34−7.54 (m, 8 H, PPh2), 7.74−7.86 (m, 3 H, PPh2 and NH).
13C{1H} NMR (CDCl3): δ 23.37 (s, 1 C, CH3CO), 38.76 (s, 1 C,
CH2), 41.89 (s, 1 C, CH2), 62.68 (s, 1 C, allyl CH2), 70.18 (s, 1 C, CH
fc), 70.32 (s, 1 C, CH fc), 71.94 (s, 1 C, CH fc), 72.00 (s, 1 C, CH fc),
73.11 (d, JPC = 8 Hz, 1 C, CH fc), 73.40 (d, JPC = 7 Hz, 1 C, CH fc),
74.57 (d, 1JPC = 46 Hz, 1 C, C−P fc), 74.63 (d, JPC = 10 Hz, 1 C, CH
fc), 77.44 (s, 1 C, C−CO fc), 82.02 (d, 2JPC = 31 Hz, 1 C, allyl CH2),
3
(m, 10 H, PPh2), 7.94 (t, JHH = 5.3 Hz, 1 H, NH). 31P{1H} NMR
(DMSO): δ 16.8 (s). IR (Nujol, cm−1): ν 3251 br m, 3085 w, 3043 w,
1823 w, 1713 w, 1627 s, 1563 w, 1538 s, 1435 m, 1386 s, 1337 m, 1302
s, 1270 m, 1240 s, 1124 m 1193 m, 1162 m, 1099 m, 1069 m, 1035 s,
998 w, 963 w, 929 m, 862 m, 841 s, 821 w, 806 m, 771 m, 753 s, 742 s,
697 s, 628 m, 608 w, 550 w, 527 s, 505 s, 471 s, 448 m, 435 m, 407 m.
ESI+ MS: m/z 674 ([M − Cl]+). Anal. Calcd for C31H35ClFeN3O2PPd
(710.29): C, 52.42; H, 4.97; N, 5.92. Found: C, 52.14; H, 5.00; N,
5.65.
2
118.88 (d, JPC = 5 Hz, 1 C, allyl CH), 128.37 (d, JPC = 10 Hz, 2 C,
CH PPh2), 128.43 (d, JPC = 10 Hz, 2 C, CH PPh2), 130.05 (s, 1 C,
CHpara PPh2), 130.39 (s, 1 C, CHpara PPh2), 132.46 (d, JPC = 12 Hz, 2
C, CH PPh2), 133.35 (d, JPC = 12 Hz, 2 C, CH PPh2), 135.60 (d, 1JPC
Complex 5e. [PdCl(η3-C3H5)]2 (36.3 mg, 0.10 mmol) and 1e (115
mg, 0.20 mmol) were reacted in 4 mL of dichloromethane, as
described above. The reaction solution was filtered, layered with
diethyl ether and hexanes, and set aside for crystallization, which
furnished 5e in the form of well-developed orange crystals (57.4 mg,
76%).
1
= 43 Hz, 1 C, Cipso PPh2), 136.00 (d, JPC = 45 Hz, 1 C, Cipso PPh2),
170.76 (s, 1 C, NHC(O)CH3), 170.82 (s, 1 C, fcC(O)NH). One of
the CH fc resonances is obscured by the solvent signal. 31P{1H} NMR
(CDCl3): δ 11.5 (s). IR (Nujol, cm−1): ν 3298 br m, 1640 s, 1538 s,
1435 w, 1288 s, 1232 m, 1177 m, 1120 w, 1097 m, 1069 m, 1031 m,
997 w, 961 w, 907 m, 874 w, 842 s, 826 s, 750 s, 797 s, 633 w, 593 m,
537 m, 514 s, 488 s, 468 s, 443 w, 437 w. ESI+ MS: m/z 645 ([M −
Cl]+), 521 ([1a + Na]+). Anal. Calcd for C30H32ClFeN2O2PPd·
0.2CH2Cl2 (698.23): C, 51.95; H, 4.68; N, 4.01. Found: C, 51.70; H,
4.87; N, 3.71.
1H NMR (CDCl3): δ 2.69 (d, J = 11.8 Hz, 1 H, allyl CH2), 2.85 (d,
J = 5.5 Hz, 1 H, allyl CH2), 3.41−3.65 (m, 4 H, CH2), 3.64 (br s, 1 H,
fc), 3.79 (br s, 1 H, fc), 3.88 (dd, J = 9.7, 13.8 Hz, 1 H, allyl CH2), 4.27
(m, 2 H, fc), 4.55 (br s, 1 H, fc), 4.57 (br s, 1 H, fc), 4.81 (dt, J = 1.4,
7.2 Hz, 1 H, allyl CH2), 5.04 (br s, 1 H, fc), 5.18 (br s, 1 H, fc), 5.68
(ddd, J = 7.6, 13.8, 18.9 Hz, 1 H, allyl CH), 6.16 (br s, 1 H, NH),
6.94−7.00 (m, 1 H, NHPh), 7.20−7.28 (m, 3 H, NHPh), 7.35−7.55
(m, 11 H, PPh2, NHPh and NH), 7.68−7.78 (m, 2 H, PPh2). 31P{1H}
NMR (CDCl3): δ 12.0 (s). IR (Nujol, cm−1): ν 3281 br m, 1697 s,
1615 s, 1552 s, 1497 m, 1438 m, 1306 s, 1202 m, 1189 w, 1169 m,
1134 w, 1103 m, 1074 w, 1030 m, 999 w, 973 w, 928 m, 891 w, 839 m,
Complex 5b. [PdCl(η3-C3H5)]2 (18.3 mg, 0.050 mmol) and 1b
(49.9 mg, 0.10 mmol) were reacted in 2 mL of dichloromethane, as
described above. Evaporation afforded 5b as an orange solid (33.0 mg,
97%). An analytical sample was obtained by recrystallization from
dichloromethane−pentane.
4143
dx.doi.org/10.1021/om5006758 | Organometallics 2014, 33, 4131−4147