M. Kaloğlu et al.
7.74 (tt, J = 7.8, 1.5 Hz, 1H, arom. H of pyridine);
9.00 (dd, J = 6.4, 1.5 Hz, 2H, arom. CHs of pyri-
dine). 13C NMR (101 MHz, CDCl3, 25 °C, TMS): δ
(ppm) = 14.98 (NCH2CH2OC6H4(OCH2CH3)-2); 21.19
(NCH2C6H4(CH3)-4); 48.00 (NCH2C6H4(CH3)-4);
5 0 . 0 1 a n d 5 0 . 8 3 ( N C H 2 C H 2 N ) ; 5 4 . 6 1
4.5.3 Dibromo‑[1‑(2‑(2‑Ethoxyphenoxy)
Ethyl)‑3‑(4‑Isopropyl‑Benzyl)Imidazolidin‑2‑Ylidene]
(Pyridine) Palladium(II), 4c
Yield 50%, 0.358 g (yellow solid); mp: 111–112 °C;
FT-IR (vC-N): 1039 and 1255 cm−1; (vC(2)-N): 1592 cm−1.
1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ (ppm)=1.17
(d, J = 6.9 Hz, 6H, NCH2C6H4(CH(CH3)2)-4); 1.30 (t,
J=7.0 Hz, 3H, NCH2CH2OC6H4(OCH2CH3)-2); 2.83 (hept,
J=6.9, 1H, NCH2C6H4(CH(CH3)2)-4); 3.39 (dd, J=11.2,
8.9 Hz, 2H, NCH2CH2OC6H4(OCH2CH3)-2); 3.94 (dd,
J = 10.7, 8.6 Hz, 2H, NCH2CH2OC6H4(OCH2CH3)-2);
3.95 (q, J = 7.0 Hz, 2H, NCH2CH2OC6H4(OCH2CH3)-2);
4.48 (dt, J = 9.1, 4.8 Hz, 4H, NCH2CH2N); 5.24 (s, 2H,
NCH2C6H4(CH(CH3)2)-4); 6.78–6.84 and 6.90–6.93 (m,
4H, arom. Hs of NCH2CH2OC6H4(OCH2CH3)-2); 7.15 (d,
J=8.0 Hz, 2H, arom. Hs of NCH2C6H4(CH(CH3)2)-4); 7.25
(ddd, J=7.8, 5.0, 1.5 Hz, 2H, arom. Hs of pyridine); 7.41
(d, J=8.0 Hz, 2H, arom. Hs of NCH2C6H4(CH(CH3)2)-4);
7.66 (tt, J = 7.7, 1.6 Hz, 1H, arom. H of pyridine);
8.92 (dd, J = 6.5, 1.5 Hz, 2H, arom. CHs of pyri-
dine). 13C NMR (101 MHz, CDCl3, 25 °C, TMS):
δ (ppm) = 15.01 (NCH2CH2OC6H4(OCH2CH3)-2);
2 4 . 0 2 ( N C H 2 C 6 H 4 ( C H ( C H 3 ) 2 ) - 4 ) ; 3 3 . 8 8
(NCH2C6H4(CH(CH3)2)-4); 48.09 (NCH2C6H4
(CH(CH3)2)-4); 50.02 and 50.87 (NCH2CH2N);
54.62 (NCH2CH2OC6H4(OCH2CH3)-2); 64.08
(NCH2CH2OC6H4(OCH2CH3)-2); 68.79 (NCH2CH2OC6
H4(OCH2CH3)-2); 113.00, 113.71, 120.99, 121.52, 148.11
and 148.69 (arom. Cs of NCH2CH2OC6H4(OCH2CH3)-2);
126.80, 128.83, 132.49 and 148.78 (arom. Cs of
NCH2C6H4(CH(CH3)2)-4); 124.51, 137.88 and 152.49
(arom. Cs of pyridine); 180.88 (Pd-Ccarbene). Elemental
analysis calcd. (%) for C28H35Br2N3O2Pd: C 47.25, H 4.96,
( N C H 2 C H 2 O C 6 H 4 ( O C H 2 C H 3 ) - 2 ) ;
6 4 . 0 4
(NCH2CH2OC6H4(OCH2CH3)-2); 68.77 (NCH2CH2OC6
H4(OCH2CH3)-2); 112.96, 113.69, 120.96, 121.50, 148.08
and 148.67 (arom. Cs of NCH2CH2OC6H4(OCH2CH3)-2);
128.83, 129.40, 132.08 and 137.79 (arom. Cs of
NCH2C6H4(CH3)-4); 124.49, 137.84 and 152.48 (arom.
Cs of pyridine); 180.89 (Pd-Ccarbene). Elemental analysis
calcd. (%) for C26H31Br2N3O2Pd: C 45.67, H 4.57, N 6.15;
1
found (%): C 45.62, H 4.67, N 6.16. (For the H NMR,
13C NMR and FT-IR spectrum of the Pd-PEPPSI-NHC
complex 4a, see ESI fle, pages S13-S14).
4.5.2 Dibromo‑[1‑(2‑(2‑Ethoxyphenoxy)
Ethyl)‑3‑(4‑Chlorobenzyl)Imidazolidin‑2‑Ylidene]
(Pyridine) Palladium(II), 4b
Yield 44%, 0.307 g (yellow solid); mp: 149–150 °C;
FT-IR (vC-N): 1045 and 1243 cm−1; (vC(2)-N): 1594 cm−1.
1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ (ppm) = 1.38
(t, J = 7.0 Hz, 3H, NCH2CH2OC6H4(OCH2CH3)-2); 3.45
(dd, J=10.4, 9.0 Hz, 2H, NCH2CH2OC6H4(OCH2CH3)-2);
4.03 (q, J = 7.1 Hz, 2H, NCH2CH2OC6H4(OCH2CH3)-2);
4.07 (dd, J = 11.1, 9.0 Hz, 2H, NCH2CH2OC6H4(OC
H2CH3)-2); 4.56 (dt, J = 21.1, 4.7 Hz, 4H, NCH2CH2N);
5.32 (s, 2H, NCH2C6H4(Cl)-4); 6.85–6.92 and 6.97–7.00
(m, 4H, arom. Hs of NCH2CH2OC6H4(OCH2CH3)-2);
7.33 (ddd, J = 7.8, 5.1, 1.4 Hz, 2H, arom. Hs of pyridine);
7.34 (d, J = 8.4 Hz, 2H, arom. Hs of NCH2C6H4(Cl)-4);
7.52 (d, J = 8.4 Hz, 2H, arom. Hs of NCH2C6H4(Cl)-4);
7.74 (tt, J = 7.7, 1.5 Hz, 1H, arom. H of pyridine);
8.99 (dd, J = 6.4, 1.5 Hz, 2H, arom. CHs of pyri-
dine). 13C NMR (101 MHz, CDCl3, 25 °C, TMS): δ
(ppm) = 14.98 (NCH2CH2OC6H4(OCH2CH3)-2); 48.03
(NCH2C6H4(Cl)-4); 50.03 and 50.97 (NCH2CH2N);
54.19 (NCH2CH2OC6H4(OCH2CH3)-2); 64.02
(NCH2CH2OC6H4(OCH2CH3)-2); 68.72 (NCH2CH2OC6
H4(OCH2CH3)-2); 112.94, 113.68, 120.95, 121.57, 148.01
and 148.66 (arom. Cs of NCH2CH2OC6H4(OCH2CH3)-2);
128.93, 130.23, 133.71 and 133.96 (arom. Cs of
NCH2C6H4(Cl)-4); 124.53, 137.92 and 152.45 (arom.
Cs of pyridine); 181.51 (Pd-Ccarbene). Elemental analysis
calcd. (%) for C25H28Br2ClN3O2Pd: C 42.64, H 4.01, N
1
N 5.90; found (%): C 47.22, H 5.13, N 5.99. (For the H
NMR, 13C NMR and FT-IR spectrum of the Pd-PEPPSI-
NHC complex 4c, see ESI fle, pages S17-S18).
4.5.4 Dibromo‑[1‑(2‑(2‑Ethoxyphenoxy)
Ethyl)‑3‑(4‑tert‑Butylbenzyl)Imidazolidin‑2‑Ylidene]
(Pyridine) Palladium(II), 4d
Yield 39%, 0.279 g (yellow solid); mp: 150–151 °C;
FT-IR (vC-N): 1041 and 1256 cm−1; (vC(2)-N): 1591 cm−1.
1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ (ppm)=1.24
(s, 9H, NCH2C6H4(C(CH3)3)-4); 1.30 (t, J = 7.0 Hz, 3H,
NCH2CH2OC6H4(OCH2CH3)-2); 3.40 (dd, J = 11.2,
9.0 Hz, 2H, NCH2CH2OC6H4(OCH2CH3)-2); 3.96 (q,
J=7.0 Hz, 2H, NCH2CH2OC6H4(OCH2CH3)-2); 3.97 (dd,
J = 10.9, 9.1 Hz, 2H, NCH2CH2OC6H4(OCH2CH3)-2);
4.49 (dt, J = 9.4, 4.7 Hz, 4H, NCH2CH2N); 5.25 (s,
2H, NCH2C6H4(C(CH3)3)-4); 6.78–6.86 and 6.91–6.93
(m, 4H, arom. Hs of NCH2CH2OC6H4(OCH2CH3)-2);
1
5.97; found (%): C 42.78, H 4.04, N 6.09. (For the H
NMR, 13C NMR and FT-IR spectrum of the Pd-PEPPSI-
NHC complex 4b, see ESI fle, pages S15-S16).
1 3