ACCEPTED MANUSCRIPT
1.4, 7.8 Hz, 1H, H6), 7.47-7.44 (m, 1H, 4H-2,6-diisopropylphenyl), 7.43 (ddd, J = 0.9, 7.4, 7.6 Hz, 1H, H7),
7.37 (dd, J = 1.4, 7.9 Hz, 1H, 3,5-H-2,6-diisopropylphenyl), 7.32 (s, 1H, H3), 7.23 (dd, J = 1.4, 7.9 Hz, 1H, 3,5-
H-2,6-diisopropylphenyl), 7.18 (d, J = 9.4 Hz, 1H, H4), 7.17 (d, J = 9.4 Hz, 1H, H5), 3.92 (d, J = 3.2 Hz, 1H,
HsC), 3.23 (bs, 1H, HaC), 3.27-3.21 (m, 1H, CH-isopropyl), 3.11-3.06 (m, 1H, m, 1H, CH-isopropyl), 2.98 (dd, J
= 1.3, 3.2 Hz, 1H, HsCl), 2.33 (bs, 1H, HaCl), 1.40 (, J = 6.8 Hz, 3H, CH3-isopropyl), 1.31 (, J = 6.8 Hz, 3H, CH3-
isopropyl), 1.12 (s, 3H, CH3-metallyl), 1.03 (, J = 6.8 Hz, 3H, CH3-isopropyl), 0.97 (, J = 6.8 Hz, 3H, CH3-
isopropyl); Minor δ = 10.16 (d, J = 8.5 Hz, 1H, H9), 7.58 (dd, J = 1.5, 7.7 Hz, 1H, H6), 7.53 (ddd, J = 1.4, 7.2,
8.5 Hz, 1H, H8), 7.47-7.44 (m, 1H, 4H-2,6-diisopropylphenyl), 7.46 (ddd, J = 0.9, 7.4, 7.6 Hz, 1H, H7), 7.35 (s,
1H, H3), 7.34 (dd, J = 1.4, 7.8 Hz, 1H, 3,5-H-2,6-diisopropylphenyl), 7.28 (dd, J = 1.4, 7.8 Hz, 1H, 3,5-H-2,6-
diisopropylphenyl), 7.18 (d, J = 9.4 Hz, 1H, H4), 7.16 (d, J = 9.4 Hz, 1H, H5), 4.06 (d, J = 3.2 Hz, 1H, HsC),
3.17 (dd, J = 1.3, 3.2 Hz, 1H, HsCl), 2.82 (bs, 1H, HaC), 2.27-2.22 (m, 2H, CH-isopropyl), 2.02 (s, 3H, CH3-
metallyl), 1.62 (bs, 1H, HaCl), 1.30 (d, J = 6.8 Hz, 3H, CH3-isopropyl), 1.24 (, J = 6.8 Hz, 3H, CH3-isopropyl),
1.12 (, J = 6.8 Hz, 3H, CH3-isopropyl), 1.10 (, J = 6.8 Hz, 3H, CH3-isopropyl). 13C NMR (151 MHz, CDCl3, two
conformers in ratio 1:0.92, 293 K) Major δ = 177.98 (4CNHC), 144.82 (2,6-4C-2,6-diisopropylphenyl), 144.68
(2,6-4C-2,6-diisopropylphenyl), 137.06 (1-4C-2,6-diisopropylphenyl), 134.29 (4C9a), 130.58 (4C3a), 130.03 (4-
C-2,6-diisopropylphenyl), 128.97 (4Cmeso), 128.93 (C8), 128.25 (C6), 126.35 (C7), 125.19 (C5), 124.97 (4C5a),
124.56 (3,5-C-2,6-diisopropylphenyl), 123.17 (3,5-C-2,6-diisopropylphenyl), 119.80 (C9), 116.95 (C3), 115.07
(C4), 70.18 (CC), 50.03 (CCl), 28.10 (CH-isopropyl), 28.08 (CH-isopropyl), 26.40 (CH3-isopropyl), 26.21 (CH3-
isopropyl), 23.06 (2*CH3-isopropyl), 21.84 (CH3-metallyl)Minor δ = 177.54 (4CNHC), 147.69 (2,6-4C-2,6-
diisopropylphenyl), 147.64 (2,6-4C-2,6-diisopropylphenyl), 137.18 (1-4C-2,6-diisopropylphenyl), 134.25 (4C9a),
130.73 (4C3a), 130.13 (4-C-2,6-diisopropylphenyl), 129.34 (4Cmeso), 128.52 (C8), 128.28 (C6), 126.30 (C7),
125.04 (C5), 124.92 (4C5a), 124.31 (3,5-C-2,6-diisopropylphenyl), 122.88 (3,5-C-2,6-diisopropylphenyl), 119.37
(C9), 116.89 (C3), 115.13 (C4), 71.53 (CC), 51.05 (CCl), 28.35 (CH-isopropyl), 28.16 (CH-isopropyl), 27.02
(CH3-isopropyl), 26.84 (CH3-isopropyl), 22.47 (CH3-isopropyl), 22.30 (CH3-isopropyl), 23.38 (CH3-metallyl).
C27H31ClN2Pd (525.43): calcd. C, 61.72; H, 5.95; N, 5.33, found: C, 61.65; H, 5.89; N, 5.37.
4.4.10. Complex 9
Prepared from 0.150 g (0.36 mmol) of e8, 0.063 g (0.172 mmol) [(allyl)PdCl]2 and 0.166 g (0.12 mmol) K2CO3
in 3 ml of dry THF for 24 hours. Purified by flash chromatography (hexanes:EtOAc = 5:1). Yield - 0.170 g
O
1
(97%) beige powder with m.p. 120 C (decomposition). H NMR (600 MHz, CDCl3, two conformers in ratio
1:0.65, 293 K) Major δ = 10.05 (d, J = 8.3 Hz, 1H, H9), 7.65-7.59 (m, 1H, H8), 7.61-7.59 (m, 1H, H6), 7.56-
7.52 (m, 1H, 4H-2,6-diisopropylphenyl), 7.52-7.49 (m, 1H, H7), 7.44-7.43 (m, 1H, 3,5-H-2,6-
diisopropylphenyl), 7.44 (s, 1H, H3), 7.31-7.29 (m, 1H, 3,5-H-2,6-diisopropylphenyl), 7.26 (d, J = 9.4 Hz, 1H,
H4), 7.25 (d, J = 9.4 Hz, 1H, H5) 5.44-5.37 (m, 1H, Hmeso), 4.34 (dd, J = 2.1, 7.4 Hz, 1H, HsC), 3.45 (d, J = 6.7
Hz, 1H, HsCl), 3.34 (m, 1H, CH-isopropyl), 3.03 (d, J = 13.5 Hz, 1H, HaC), 2.32 (m, 1H, CH-isopropyl), 1.66 (d,
J = 12.0 Hz, 1H, HaCl), 1.49 (d, J = 6.7 Hz, 1H, CH3-isopropyl), 1.31 (d, J = 6.7 Hz, 1H, CH3-isopropyl), 1.19
(d, J = 6.7 Hz, 1H, CH3-isopropyl), 1.12 (d, J = 6.7 Hz, 1H, CH3-isopropyl); Minor δ = 10.42 (d, J = 8.3 Hz, 1H,
H9), 7.70-7.67 (m, 1H, H8), 7.69-7.37 (m, 1H, H6), 7.56-7.52 (m, 1H, 4H-2,6-diisopropylphenyl), 7.55-7.52 (m,
1H, H7), 7.41-7.49 (m, 1H, 3,5-H-2,6-diisopropylphenyl), 7.40 (s, 1H, H3), 7.33-7.31 (m, 1H, 3,5-H-2,6-
28