Supporting Information

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1 Supporting Information Wiley-VCH Weinheim, Germany

2 Sandwich Complexes Containing Bent Palladium ains Yasuki Tatsumi, Katsunori Shirato, Tetsuro Murahashi,* Sensuke Ogoshi and Hideo Kurosawa* Department of Applied emistry, Graduate School of Engineering, Osaka University, & PRESTO, Japan Science and Technology Agency (JST), Suita, Osaka, , Japan Experimental Details General Consideration. All manipulations were conducted under a nitrogen atmosphere using standard Schlenk or drybox techniques. 1 H, 13 C nuclear magnetic resonance spectra were recorded on 270 (JEOL GSX-270) and 400 MHz (JEOL GSX-400) instruments. The chemical shifts were referenced to the residual resonances of deuterated solvents. Elemental analyses were performed at the Analytical nter, Faculty of Engineering, Osaka University. X-ray crystal data were collected by Rigaku RAXIS-RAPID Imaging Plate diffractometer. Unless specified, all reagents were purchased from commercial suppliers and used without purification. Ethanol was distilled from Mg/I 2 prior to use. [Pd 2 (CH 3 CN) 6 ][BF 4 ] [3b] 2, [Pd 4 (perylene) 2 (CH 3 CN) 2 ][BAr f ] 2 (4) [6] and NaBAr f were prepared according to the literature. N. A. Yakelis, R. G. Bergman, Organometallics 2005, 24, Synthesis of 1,2-bis(4-phenyl-1,3-butadinenyl)benzene [o-bpbb] (2) To a solution of o-xylylene-bis(triphenylphosphonium chloride) (15.0 g, 21.4 mmol) and cinnamaldehyde (6.76 ml, 53.6 mmol) in 80 ml of ethanol was slowly added a solution of sodium ethoxide (3.26 g, 47.9 mmol) dissolved in 96 ml of ethanol. After stirring overnight the yellow solid was filtered and washed with water (50 ml) and ethanol (30 ml), then dried under reduced pressure. Recrystallization from C 6 H 6 /hexane

3 gave pale-yellow crystal of o-bpbb (3.60 g, 50% yield). Anal. lcd. for C 26 H 22 : C, 93.37; H, Found C, 93.10; H, This material was prepared from o-xylylene dichloride according to the literature: R. N. McDonald, T. W. mpbell, J. Org. em. 1959, 24, Synthesis of o-bpbb-pd 4 complex [Pd 4 (o-bpbb) 2 ][BAr f ] 2 (5) To a suspension of [Pd 2 (CH 3 CN) 6 ][BF 4 ] 2 (170.2 mg, mmol) in C 2 H 4 Cl 2 were added o-bpbb (450.0 mg, 1.35 mmol) and Pd 2 (dba) 3 CHCl 3 (278.5 mg, mmol), the mixture was stirred overnight at room temperature. The precipitate was collected, washed with benzene and dried under vacuum to give brown powder of [Pd 4 (o-bpbb) 2 ][BF 4 ] 2 (5-BF 4 ) (288.3 mg, 85% yield). Anal. lcd. for C 52 H 44 B 2 F 8 Pd 4 0.5(C 2 H 4 Cl 2 ): C, 48.31; H, Found C, 48.33; H, To a suspension of 5-BF 4 (200.0 mg, mmol) in CH 2 Cl 2 was added NaBAr f (279.5 mg, mmol), and the solution was stirred for 10 min. After filtration, slow diffusion of n-hexane into the filtrate gave [Pd 4 (o-bpbb) 2 ][BAr f ] 2 (5) as red-brown crystals (360.8 mg, 81% yield). 1 H NMR for coordinated o-bpbb (270 MHz, CD 2 Cl 2, 25 ºC) δ 7.31 (2H, t, J = 9.6 Hz, ), 6.93 (4H, t, J = 7.8 Hz, ), 6.68 (4H, d, J = 7.3 Hz, ), 6.38 (2H, d, J = 12.9 Hz, ), 6.03 (2H, m, ), 5.74 (2H, m, ), 4.50 (4H, Hf+), 1.91 (2H, d, J = 11.7 Hz, ). 13 C{ 1 H} NMR for coordinated o-bpbb (100.5 MHz, CD 2 Cl 2, 25 ºC) δ (Cd), (), (), (), (), (), (), 99.0 (), 94.8 (), 83.8 (), 77.5 (). Anal. lcd. for C 116 H 68 B 2 F 48 Pd 4 : C, 49.39; H, Found C, 49.03; H, Cd Hf Mirror Plane

4 Synthesis of 1,4-bis(4-phenyl-1,3-butadienyl)benzene [p-bpbb]-pd 4 complex (6) To a solution of [Pd 4 (perylene) 2 (CH 3 CN) 2 ][BAr f ] 2 (4) (260.2 mg, mmol) in CH 2 Cl 2 was added p-bpbb (160.0 mg, mmol), and the mixture was stirred Ht Hu Hr Ct Cu Cd Hp Cr Cs Cv Hv Cp Cq Ct Cu Hf Cn Co Hq Ht Hu Ho Cl Cm Hl overnight at room temperature. The precipitate was collected, washed with CH 2 Cl 2 and dried under vacuum to give brown powder of [Pd 4 (p-bpbb) 2 ][BAr f ] 2 (6) (218.5 mg, 81% yield). 1 H NMR for coordinated p-bpbb (270 MHz, acetone-d 6, 25 ºC) δ (10H terminal Ph,,b,c,t,u,v), 7.12 (1H, dd, J = 15.7 Hz, J = 10.8 Hz, Hq), 6.61 (1H, d, J = 15.7 Hz, Hr), 6.30 (1H, d, J = 13.2 Hz, ), 6.19 (1H, d, J = 13.2 Hz, Ho), 6.12 (1H, dd, J = 13.2 Hz, J = 11.7 Hz, Hf), 5.75 (1H, dd, J = 13.2 Hz, J = 10.8 Hz, Hp), 4.93 (1H, d, J = 7.6 Hz, Hl), 4.84 (1H, d, J = 7.3 Hz, Hm), 4.54 (1H, d, J = 12.4 Hz, ), 3.90 (1H, d, J = 9.2 Hz, ), 3.42 (1H, d, J = 9.2 Hz, ), 3.26 (1H, t, J = 11.5 Hz, ). NOE were observed for (13%), Hl (13%), Hm Ho (12 %) and Hp (16%). 13 C{ 1 H} NMR for coordinated p-bpbb (100.5 MHz, acetone-d 6, 25 ºC) δ (Cr), (terminal Ph,b,c,t,u,v), (Cd), (Cs), (Cq), (, ), (Cp), (), 98.1 (), 97.4 (Cn), 96.1 (Co), 94.9 (), 89.8 (Cl), 86.3 (), 82.9 (), 81.5 (Cm). Anal. lcd. for C 116 H 68 B 2 F 48 Pd 4 CH 2 Cl 2 : C, 48.36; H, Found C, 48.05; H, Hm Synthesis of (p-bpbb)-pd 5 complex (7) [Pd 4 (p-bpbb) 2 ][BAr f ] 2 (6) (10.0 mg, 17.7 µmol) was dissolved in ClCH 2 CH 2 Cl/CH 3 CN (v/v = 1/1), then the solution was stirred for 1 day at room temperature. Subsequently, the solution was filtered, and slow diffusion of pentane into the filtrate gave reddish-orange microcrystals of [Pd 5 (p-bpbb) 2 ][BAr f ] 2 (7) (2.9 mg, 27% yield). 1 H NMR for coordinated p-bpbb (270 MHz, CD 2 Cl 2, 25 ºC) δ 7.49 (2H, t, J = 7.3 Hz, ), 7.14 (4H, m, ), 6.99 (4H, d, J = 8.7 Hz, ), 5.91 (2H, d, J = 13.7 Hz, ), 5.64 (2H, dd, J = 13.8 Hz, J = 10.9 Hz, Hf), 4.39 (2H, s, ), 4.05 (2H, d, J = 12.0 Hz, ), 2.49 (2H, s, ), 2.36 (2H, t, J = 11.5 Hz, ). 13 C{ 1 H} NMR for coordinated p-bpbb (100.5 MHz, CD 2 Cl 2, 25 ºC) δ (Cd), (), (), (),

5 117.3 (), (), 95.6 (), 95.4 (), 84.6 (), 83.8 (), 79.0 (). Anal. lcd. for C 116 H 68 B 2 F 48 Pd 5 ClCH 2 CH 2 Cl CH 3 CN: C, 46.99; H, 2.46; N, 0.46 Found: C, 47.08; H, 2.52; N, Cd Hf Mirror Plane Synthesis of 1,4-bis(2-phenylethenyl)benzene [p-bpeb]-pd 4 complex (8) To a solution of [Pd 4 (perylene) 2 (CH 3 CN) 2 ][BAr f ] 2 (4) (290.9 mg, mmol) in ClCH 2 CH 2 Cl was added p-bpeb (150.0 mg, mmol), and the mixture was heated at reflux for 1.5 h. The solution was filtered off, then the solvent was removed in vacuo. Recrystallization from CH 2 Cl 2 /hexane gave dark red microcrystal of 8 containing 1 equiv. of perylene as formulated as {[Pd 4 (BPEB) 2 ][BAr f ] 2 } perylene (218.3 mg, 70% yield). 1 H NMR for coordinated p-bpeb (270 MHz, CD 2 Cl 2, 25 ºC) δ 7.92 (1H, t, J = 7.4 Hz, ), 7.82 (1H, br, ), 7.46 (1H, t, J = 7.6 Hz, Ht), 7.30 (1H, br, Hd), 7.15 (2H, t, J = 7.8 Hz, Hs), 7.04 (2H, d, J = 7.3 Hz, Hr), 6.90 (overlapped 2H, br, &), 5.94 (1H, d, J = 14.4 Hz, Ho), 5.57 (1H, d, J = 14.2 Hz, Hp), 4.48 (1H, d, J = 7.3 Hz, Hm), 4.37 (1H, d, J = 7.1 Hz, Hl), 4.13 (1H, d, J = 12.5 Hz, ), 3.71 (1H, d, J = 9.5 Hz, ), 3.48 (1H, d, J = 12.7 Hz, ), 3.29 (1H, d, J = 9.5 Hz, ). NOE were observed for (16%), Hl (9%), Hm Ho (10%) and Hp (15%). 13 C{ 1 H} NMR for coordinated p-bpeb (100.5 MHz, CD 2 Cl 2, 25 ºC) δ (), (), (Cd), (Ct), (Cs), (Cq), (Cr), (), (), (), (), (Cp), (), 95.9 (Cn), 92.9 (), 92.5 (Co), 89.4 (Cl), 81.2 (), 80.5 (Cm), 76.7 (). Anal. lcd. for C 128 H 72 B 2 F 48 Pd 4 CH 2 Cl 2 : C, 50.73; H, Found C, 50.76; H, Hr Hs Hp Cr Cs Cp Cq Ct Ht Hd Cd Cn Co Cr Cs Ho Hr Hs Cl Cm Hl Hm

6 Formation of (p-bpeb)-pd 5 complex (9) To a solution of {[Pd 4 (p-bpeb) 2 ][BAr f ] 2 } perylene (8) (5.0 mg, 1.84 µmol) in CD 2 Cl 2, was added Pd 2 (dba) 3 CH 3 Cl (1.0 mg, µmol), and {[Pd 5 (p-bpeb) 2 ][BArf] 2 } (10) was formed in 50% NMR yield. The molar ratio of 8 and 9 (ca. 1 : 1) remained unchanged after 7 days. 1 H NMR for coordinated p-bpeb (270 MHz, CD 2 Cl 2, 25 ºC) δ (10H,,b,c), 4.40 (2H, s, Hi), 4.18 (2H, d, J = 12.7 Hz, Hf), 3.23 (2H, d, J = 12.5Hz, ), 2.83 (2H, s, ). Clear assignment of, and could not be performed due to overlapping of these 1 H peaks with some aromatic 1 H peaks of complex C{ 1 H} NMR for coordinated p-bpeb (100.5 MHz, CD 2 Cl 2, 25 ºC) δ (), (Cd), 94.9 (), 84.4 (), 78.8 (), 73.9 (). Accurate chemical shifts of, and were not determined due to overlapping of these signals with some 13 C signals of complex 8. Cd Hf Hi Mirror Plane Crystal structure determination All data were obtained on a Rigaku RAXIS-RAPID Imaing Plate diffractometer with graphite monochromated Mo-Kα radiation. lculations were carried out with the CrystalStructure crystallographic software package of Rigaku. The structure was solved by direct methods or Patterson methods and the function minimized being ( Fo - Fc ) 2. Some carbon and fluorine atoms at CF 3 groups on BAr - f were refined isotropically in the crystal of 5 since the corresponding CF 3 groups were disordered even at 133K. The nonhydrogen atoms except for above C, F atoms as well as those of solvent molecules were refined anisotropically. All hydrogens were sited at calculated positions. Crystal data for 5: C 122 H 80 B 2 F 48 Cl 12 Pd 4, M = , monoclinic, space group C2/c (no.

7 15), a = (1) Å, b = (2) Å, c = (2) Å, β = (3), V = 13313(1) Å 3, Z = 4, F(000) = 6568, Dc = g cm 3, (MoK ) = 8.87 cm 1, Temperature = 133 K, 835 variables refined with reflections with I > 3s (I) to R1 = Crystal data for 7: C 124 H 83 B 2 NF 48 Cl 6 Pd 5, M = , monoclinic, space group P2 1 /n (no. 14), a = (3) Å, b = (4) Å, c = (4) Å, β = (6), V = (3) Å 3, Z = 4, F(000) = 6432, Dc = g cm 3, (MoK ) = 9.79 cm 1, Temperature = 133 K, 1668 variables refined with reflections with I > 3s (I) to R1 =