Supporting Information. for

Transcription

1 Supporting Information for "Inverse-Electron-Demand" Ligand Substitution in Palladium(0) Olefin Complexes Shannon S. Stahl,* Joseph L. Thorman, Namal de Silva, Ilia A. Guzei, and Robert W. Clark Department of Chemistry, University of Wisconsin-Madison, 1101 University Ave., Madison, WI Experimental General Procedures. All manipulations were performed under an inert atmosphere of nitrogen using a H. M. Braun glovebox. All solvents were rigorously degassed and dried prior to use. Methylene chloride-d 2, diethyl ether, hexanes, methylene chloride, and toluene were dried by passage through a column of activated alumina. (bc)pd(dba) was prepared according to the published procedure. 1 The following compounds, β-nitrostyrene derivatives, bathocuproine (Aldrich) were obtained from commercial sources and used as received. 1 H NMR data were recorded at 27.0 ºC, unless otherwise stated using a Varian Unity ( 1 H: 500 MHz), a Bruker Avance ( 1 H: 360 MHz), or Bruker Inova ( 1 H: 300 MHz) spectrometers. Chemical shifts were referenced to residual protons in the deuterated solvent (i.e., CDHCl 2 : δ 5.32). Synthesis of (bc)pd(ns X ) derivatives. Each of these complexes (bc = bathocuproine, 2,9- dimethyl-4,7-diphenyl-1,10-phenananthroline; ns X = p-x-trans-β-nitrostyrene, X = CH 3 O, CH 3, H, Br, CF 3 ) were all synthesized in an analogous manner. Representative procedure for (bc)pd(ns CH3 ): In a glovebox at ambient temperature (ca. 23 C), a 100 ml round bottom flask was charged with 1 Stahl, S. S.; Thorman, J. L.; Nelson, R. C.; Kozee, M. A. J. Am. Chem. Soc. 2001, 123,

2 (bc)pd(dba) (215.5 mg, mmol), p-methyl-trans-β-nitrostyrene (60.6 mg, 0.37 mmol), and dichloromethane (ca. 10 ml) to give a light orange solution. After 10 minutes the solution was filtered over a celite pad and the filtrate reduced in volume under vacuum (ca. 1 ml). Et 2 O (ca. 10 ml) was then added and placed in freezer (-30 C) for 30 minutes, after which the mixture was filtered. The solid was then dissolved in minimal CH 2 Cl 2 (ca. 2 ml) and hexanes added (ca. 15 ml), mixed thoroughly and placed in the freezer (-30 C) for 15 minutes. This solution was then filtered and dried under vacuum to yield pure product (153 mg, 71 % yield). Analytically pure samples could be obtained by layering a toluene solution with hexanes (1:2 V:V), allowing to stand at -25 C, filtering, and drying the solid in vacuo. Crystals suitable for X-ray diffraction analysis were obtained by dissolving solid sample in a minimum of CH 2 Cl 2, layering with hexane and allowing to stand undisturbed at 30 C. Crystallographic data are provided below. 1 H NMR (δ, CD 2 Cl 2, 360 MHz): (bc)pd(ns OCH3 ):7.81 (m, 2H, bc Ar-H), 7.69 (s, 1H, bc Ar-H), 7.57 (s, 1H, bc Ar-H), 7.53 (m, 10H, bc Ar-H), 7.33 (d, 2H, 3 J H-H = 9 Hz, ns OCH3 Ar-H), 6.68 (d, 2H, 3 J H-H = 9 Hz, ns OCH3 Ar-H), 5.94 (d, 2H, 3 J H-H = 8 Hz, ns OCH3 CH=CH), 4.64 (d, 2H, 3 J H-H = 8 Hz, ns OCH3 CH=CH), 3.68 (s, 3H, ns OCH3 CH 3 ).3.11 (s, 3H, bc CH 3 ), 2.81 (s, 3H, bc CH 3 ). (bc)pd(ns CH3 ):7.79 (m, 2H, bc Ar-H), 7.71 (s, 1H, bc Ar-H), 7.58 (s, 1H, bc Ar-H), 7.54 (m, 10H, bc Ar-H), 7.36 (d, 2H, 3 J H-H = 8 Hz, ns CH3 Ar-H), 6.96 (d, 2H, 3 J H-H = 8 Hz, ns CH3 Ar-H), 5.96 (d, 2H, 3 J H-H = 8 Hz, ns CH3 CH=CH), 4.73 (d, 2H, 3 J H-H = 8 Hz, ns CH3 CH=CH), 3.21 (s, 3H, bc CH 3 ), 2.89 (s, 3H, bc CH 3 ), 2.17 (s, 3H, ns CH3 CH 3 ). (bc)pd(ns H ):7.80 (m, 2H, bc Ar-H), 7.72 (s, 1H, bc Ar-H), 7.59 (s, 1H, bc Ar-H), 7.6 (m, 12H, bc Ar-H and ns H Ar-H), 7.13 (m, 3H, ns H Ar-H), 5.98 (d, 2H, 3 J H-H = 8 Hz, ns H CH=CH), 4.74 (d, 2H, 3 J H-H = 8 Hz, ns H CH=CH), 3.21 (s, 3H, bc CH 3 ), 2.88 (s, 3H, bc CH 3 ). (bc)pd(ns Br ): 7.80 (m, 2H, bc Ar-H), 7.70 (s, 1H, bc Ar-H), 7.55 (m, 11H, bc Ar-H), 7.38 (d, 2H, 3 J H-H = 8 Hz, ns Br Ar-H), 7.27 (d, 2H, 3 J H-H = 8 Hz, ns Br Ar-H), 5.98 (d, 2H, 3 J H-H = 7 Hz, ns Br CH=CH), 4.76 (d, 2H, 3 J H-H = 7 Hz, ns Br CH=CH), 3.24 (s, 3H, bc CH 3 ), 2.88 (s, 3H, bc CH 3 ). (bc)pd(ns CF3 ): 7.79 (m, 2H, bc Ar-H), 7.68 (s, 1H, bc Ar-H), 7.5 (m, 15H, bc Ar-H and ns CF3 Ar- 2

3 H), 6.00 (d, 2H, 3 J H-H = 8 Hz, ns CF3 CH=CH), 4.68 (d, 2H, 3 J H-H = 8 Hz, ns CF3 CH=CH), 3.10 (s, 3H, bc CH 3 ), 2.78 (s, 3H, bc CH 3 ), 13 C NMR (δ, CD 2 Cl 2, 90.5 MHz): (bc)pd(ns OCH3 ): 161.9, 161.7, 157.6, 150.5, 150.4, 147.2, 137.5, 130.1, 130.0, 129.6, 129.4, 128.3, 126.4, 126.3, 126.2, 124.0, 123.9, 81.33, 55.7, 47.0, 29.9, (bc)pd(ns CH3 ): 161.9, 161.7, 150.5, 150.3, 147.2, 146.6, 142.2, 137.6, 134.6, 130.1, 130.0, 129.6, 129.4, 127.2, 126.4, 126.2, 124.0, 123.9, 81.4, 47.2, 30.0, 28.8, (bc)pd(ns H ): 161.9, 161.7, 150.5, 150.4, 147.2, 146.6, 145.4, 137.6, 137.5, 130.1, 130.0, 129.6, 129.4, 129.3, 128.9, 127.3, 126.4, 126.2, 124.9, 124.0, 123.9, 81.3, 47.2, 30.0, (bc)pd(ns Br ): 162.0, 161.6, 150.6, 150.5, 147.2, 146.7, 144.8, 137.5, 137.4, 131.8, 130.1, 130.0, 129.6, 129.4, 129.4, 128.9, 126.4, 126.4, 126.2, 124.1, 124.0, 117.8, 80.9, 46.1, 30.1, (bc)pd(ns CF3 ): 162.0, 161.6, 150.7, 150.6, 150.0, 147.2, 143.4, 137.4, 135.5, 131.0, 130.0, 129.7, 129.5, 129.4, 128.9, 127.3, 126.4, 126.2, 126.1, 124.8, 124.0, 80.8, 46.0, 30.1, X-ray: (see data below). Line-broadening investigations: All data were collected on a Varian Unity 500 with sw=8000, nt=32, d1=5 s. A representative run follows: An NMR tube was charged with 1,3,5-tritert-butylbenzene (2.92 µmol), (bc)pd(ns CF3 ) (3.6 mg, 5.21 µmol), ns CF3 (7.35 mg, µmol), and CD 2 Cl 2 (555 µl total volume). Spectra were obtained at the desired temperature after allowing at least 25 min for temperature equilibration. Lineshape simulations for the methine resonances of the bound olefin were carried out with GNMR v4.1 and compared with the experimental spectra to calculate the line width at half height. Equilibrium constant investigations: All data were collected on the Bruker Avance 360 with ds=2, sw=15 ppm, ns=32, d1=10 s. Baseline correction and line broadening, 0.3 Hz, were utilized. A representative run follows: An NMR tube was charged with 1,3,5-tri-tert-butylbenzene (3.06 µmol), (bc)pd(ns CF3 ) (3.9 mg, 5.68 µmol), ns Br (7.4 mg, µmol), and CD 2 Cl 2 (489 µl total 3

4 volume). Spectra were taken at the desired temperature after allowing at least 25 min for temperature equilibration. Integrations of the bound olefin resonances were used to obtain the equilibrium constants. UV-visible Kinetics of Olefin Exchange. UV-visible data were acquired on a pccontrolled Cary 3E spectrophotometer with WinUV 2.01 software. Temperature was maintained with a Cary 1x1 peltier temperature controller. A representative kinetics experiment follows: Stock solutions of (bc)pd(ns CH3 ) (1mM) and ns CF3 (2mM) were prepared in the glovebox and removed from the glovebox in a schlenk tube equipped with a 4mm Kontes Teflon valve. The (bc)pd(ns CH3 ) stock solution was maintained at -78 C in between kinetic runs to avoid decomposition, which takes place slowly over several hours in solution. A gastight UV-visible cell equipped with a side-arm reservoir was employed to allow both stock solutions to be added to the cell under a nitrogen atmosphere prior to initiating the reaction. The palladium stock solution (300 µl) and CH 2 Cl 2 (2.55 ml) were added via syringe to the UV-visible cell, and the ns CF3 solution (150 µl) was added to the side-arm. After obtaining the initial absorbance reading of the (bc)pd(ns CH3 ) solution, the contents of the cell and sidearm were mixed rapidly and single-wavelength (425nm) data collection was initiated. Most reactions were complete (> 5 half-lives) within 5 minutes. A text file of the data was imported into Microsoft Excel for data fitting. For data fitting, a kinetic model based on bimolecular approach to equilibrium was employed, and the data were fit by minimizing the sum of the squared deviations between the experimental data and a fourth-order Runge-Kutta numerical simulation of bimolecular kinetic model. The equilibrium constants for olefin binding were required for fitting and these data were obtained by 1 H NMR experiments, as described above. A representative data set and fit is shown in Figure 3 of the main text. 4

5 X-ray data for (bc)pd(ns H ), (bc)pd(ns CH3 ), (bc)pd(ns Br ). (bc)pd(ns H ): Data Collection An orange air-sensitive crystal with approximate dimensions 0.15 x 0.08 x 0.03 mm 3 was selected under oil under ambient conditions and attached to the tip of a glass capillary. The crystal was mounted in a stream of cold nitrogen at 173(2) K and centered in the X-ray beam by using a video camera. The crystal evaluation and data collection were performed on a Bruker CCD-1000 diffractometer with Mo Kα (λ = Å) radiation and the diffractometer to crystal distance of 4.9 cm. The initial cell constants were obtained from three series of ω scans at different starting angles. Each series consisted of 20 frames collected at intervals of 0.3º in a 6º range about ω with the exposure time of 30 seconds per frame. A total of 44 reflections was obtained. The reflections were successfully indexed by an automated indexing routine built in the SMART program. The final cell constants were calculated from a set of 3913 strong reflections from the actual data collection. The data were collected by using the hemisphere data collection routine. The reciprocal space was surveyed to the extent of a full sphere to a resolution of 0.80 Å. A total of 15900data were harvested by collecting three sets of frames with 0.3º scans in ω with an exposure time 120 sec per frame. These highly redundant datasets were corrected for Lorentz and polarization effects. The absorption correction was based on fitting a function to the empirical transmission surface as sampled by multiple equivalent measurements. 2 Structure Solution and Refinement The systematic absences in the diffraction data were uniquely consistent for the space group P2 1 /n that yielded chemically reasonable and computationally stable results of refinement. 3 A successful solution by the direct methods provided most non-hydrogen atoms from the E-map. The remaining non-hydrogen atoms were located in an alternating series of least-squares cycles and difference Fourier maps. All non-hydrogen atoms were refined with anisotropic displacement coefficients. All hydrogen atoms were included in the structure factor calculation at idealized positions and were allowed to ride on the neighboring atoms with relative isotropic displacement coefficients. All phenyl groups were refined with idealized geometries. The phenyl groups at atom C(17) is disordered over two positions in a 55:45 ratio. There is also 0.5 solvate molecule of dichloromethane disordered over a crystallographic center per Pd complex in the lattice. The solvate molecule was refined with soft constraints and restraints. The final least-squares refinement of 317 parameters against 4493 data resulted in residuals R (based on F 2 for I 2σ) and wr (based on F 2 for all data) of and , respectively. The final difference Fourier map was featureless. The ORTEP diagrams are drawn with 30% probability ellipsoids. 2 Blessing, R.H. Acta Cryst. 1995, A51, All software and sources of the scattering factors are contained in the SHELXTL (version 5.1) program library (G. 5

6 Figure S1. ORTEP drawing of the β-nitrostyrene adduct of bathocuproine-coordinated palladium(0), (bc)pd(ns H ). Sheldrick, Bruker Analytical X-Ray Systems, Madison, WI). 6

7 Table S1. Crystal data and structure refinement for (bc)pd(ns H ). Identification code sta05 Empirical formula C 34 H 27 N 3 O 2 Pd 1/2 CH 2 Cl 2 Formula weight Temperature 173(2) K Wavelength Å Crystal system Monoclinic Space group P2 1 /n Unit cell dimensions a = (14) Å α= 90. b = (3) Å β= (3). c = (3) Å γ = 90. Volume (7) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1340 Crystal size 0.15 x 0.08 x 0.03 mm 3 Theta range for data collection 2.29 to Index ranges -7<=h<=11, -20<=k<=16, -19<=l<=19 Reflections collected Independent reflections 4493 [R(int) = ] Completeness to theta = % Absorption correction Empirical with SADABS Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4493 / 8 / 317 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 7

8 Table S2. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for (bc)pd(ns H ). U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) Pd(1) 2840(1) 1301(1) 3808(1) 42(1) Cl(1) 6293(5) 384(3) 217(4) 160(2) O(1) 4595(10) 1417(6) 1853(5) 102(3) O(2) 4938(9) 2337(6) 2648(7) 93(3) N(1) 2130(8) 1165(4) 4985(5) 44(2) N(2) 3527(8) 184(4) 4141(4) 38(2) N(3) 4216(13) 1818(7) 2378(6) 71(3) C(1) 1679(16) 2488(6) 5216(8) 102(5) C(2) 1564(13) 1668(6) 5433(7) 60(3) C(3) 922(11) 1460(6) 6117(6) 58(3) C(4) 788(10) 716(6) 6330(6) 44(3) C(5) 139(7) 521(4) 7073(3) 44(3) C(6) -1186(7) 791(3) 7177(4) 55(3) C(7) -1826(6) 615(4) 7864(5) 62(3) C(8) -1142(8) 170(4) 8448(4) 64(3) C(9) 183(8) -99(3) 8344(3) 56(3) C(10) 823(5) 76(4) 7656(4) 49(3) C(11) 1373(10) 163(5) 5838(6) 41(2) C(12) 1265(10) -623(5) 5971(6) 42(3) C(13) 1991(10) -1112(5) 5550(6) 46(3) C(14) 2834(10) -865(5) 4946(5) 40(2) C(15) 2817(9) -109(5) 4740(5) 33(2) C(16) 2071(10) 427(5) 5193(5) 38(2) C(17) 3693(9) -1353(5) 4537(5) 40(2) C(18) 3866(8) -2151(3) 4793(4) 55(2) C(19) 4290(10) -2405(4) 5553(4) 55(2) C(20) 4428(10) -3170(4) 5700(4) 55(2) C(21) 4141(9) -3683(3) 5087(5) 55(2) C(22) 3718(11) -3429(4) 4327(4) 55(2) C(23) 3580(10) -2663(4) 4180(3) 55(2) C(18A) 3646(8) -2182(3) 4665(4) 55(2) C(19A) 4775(7) -2475(4) 5124(5) 55(2) C(20A) 4793(7) -3229(4) 5338(5) 55(2) C(21A) 3682(9) -3691(3) 5092(5) 55(2) C(22A) 2552(8) -3398(4) 4633(6) 55(2) C(23A) 2534(8) -2644(4) 4420(6) 55(2) C(24) 4458(10) -1048(6) 3971(6) 45(3) C(25) 4344(10) -278(6) 3768(5) 41(3) C(26) 5157(10) 47(6) 3130(6) 52(3) C(27) 2889(11) 1697(6) 2675(6) 54(3) C(28) 2266(10) 2249(6) 3147(6) 48(3) C(29) 778(6) 2474(4) 3040(4) 47(3) C(30) 392(8) 3136(4) 3402(4) 63(3) C(31) -985(10) 3369(4) 3326(5) 89(5) C(32) -1976(6) 2941(6) 2889(6) 97(5) C(33) -1589(8) 2280(6) 2527(5) 91(4) C(34) -213(9) 2046(4) 2602(5) 69(3) C(35) 4527(16) 344(18) 307(19) 142(14) 8

9 Table S3. Bond lengths [Å] and angles [ ] for (bc)pd(ns H ). Pd(1)-C(27) 2.040(10) C(14)-C(17) 1.415(12) Pd(1)-C(28) 2.075(9) C(15)-C(16) 1.447(12) Pd(1)-N(2) 2.156(7) C(17)-C(24) 1.362(12) Pd(1)-N(1) 2.161(8) C(17)-C(18) 1.491(10) Cl(1)-C(35) 1.726(14) C(17)-C(18A) 1.493(10) Cl(1)-C(35)# (14) C(18)-C(19) O(1)-N(3) 1.215(12) C(18)-C(23) O(2)-N(3) 1.224(12) C(19)-C(20) N(1)-C(2) 1.317(12) C(20)-C(21) N(1)-C(16) 1.364(11) C(21)-C(22) N(2)-C(25) 1.330(11) C(22)-C(23) N(2)-C(15) 1.368(11) C(18A)-C(19A) N(3)-C(27) 1.427(14) C(18A)-C(23A) C(1)-C(2) 1.510(14) C(19A)-C(20A) C(2)-C(3) 1.400(14) C(20A)-C(21A) C(3)-C(4) 1.380(13) C(21A)-C(22A) C(4)-C(11) 1.431(12) C(22A)-C(23A) C(4)-C(5) 1.483(11) C(24)-C(25) 1.416(13) C(5)-C(6) C(25)-C(26) 1.494(12) C(5)-C(10) C(27)-C(28) 1.427(14) C(6)-C(7) C(28)-C(29) 1.490(11) C(7)-C(8) C(29)-C(30) C(8)-C(9) C(29)-C(34) C(9)-C(10) C(30)-C(31) C(11)-C(16) 1.404(13) C(31)-C(32) C(11)-C(12) 1.423(12) C(32)-C(33) C(12)-C(13) 1.352(12) C(33)-C(34) C(13)-C(14) 1.421(13) C(35)-Cl(1)# (14) C(14)-C(15) 1.390(12) 9

10 C(27)-Pd(1)-C(28) 40.6(4) C(27)-Pd(1)-N(2) 122.2(4) C(28)-Pd(1)-N(2) 162.6(4) C(27)-Pd(1)-N(1) 158.4(4) C(28)-Pd(1)-N(1) 119.5(4) N(2)-Pd(1)-N(1) 76.8(3) C(35)-Cl(1)-C(35)#1 66.1(15) C(2)-N(1)-C(16) 118.8(9) C(2)-N(1)-Pd(1) 128.7(7) C(16)-N(1)-Pd(1) 111.4(6) C(25)-N(2)-C(15) 117.5(8) C(25)-N(2)-Pd(1) 129.0(6) C(15)-N(2)-Pd(1) 112.5(6) O(1)-N(3)-O(2) 121.3(13) O(1)-N(3)-C(27) 119.7(13) O(2)-N(3)-C(27) 119.0(11) N(1)-C(2)-C(3) 121.5(10) N(1)-C(2)-C(1) 118.5(10) C(3)-C(2)-C(1) 120.0(10) C(4)-C(3)-C(2) 121.6(9) C(3)-C(4)-C(11) 117.4(9) C(3)-C(4)-C(5) 119.9(9) C(11)-C(4)-C(5) 122.6(8) C(6)-C(5)-C(10) C(6)-C(5)-C(4) 118.6(6) C(10)-C(5)-C(4) 121.4(6) C(5)-C(6)-C(7) C(6)-C(7)-C(8) C(9)-C(8)-C(7) C(8)-C(9)-C(10) C(9)-C(10)-C(5) C(16)-C(11)-C(12) 119.7(8) C(16)-C(11)-C(4) 117.0(9) C(12)-C(11)-C(4) 123.3(9) C(13)-C(12)-C(11) 120.2(9) C(12)-C(13)-C(14) 121.8(9) C(15)-C(14)-C(17) 117.9(9) C(15)-C(14)-C(13) 118.7(9) C(17)-C(14)-C(13) 123.3(9) N(2)-C(15)-C(14) 123.8(9) N(2)-C(15)-C(16) 115.8(8) C(14)-C(15)-C(16) 120.3(8) N(1)-C(16)-C(11) 123.6(9) N(1)-C(16)-C(15) 117.9(8) C(11)-C(16)-C(15) 118.5(8) C(24)-C(17)-C(14) 117.8(9) C(24)-C(17)-C(18) 121.8(9) C(14)-C(17)-C(18) 120.0(8) C(24)-C(17)-C(18A) 121.3(9) C(14)-C(17)-C(18A) 120.7(8) C(18)-C(17)-C(18A) 11.41(8) C(19)-C(18)-C(23) C(19)-C(18)-C(17) 126.5(4) C(23)-C(18)-C(17) 113.5(5) C(20)-C(19)-C(18) C(21)-C(20)-C(19) C(20)-C(21)-C(22) C(23)-C(22)-C(21)

11 C(22)-C(23)-C(18) C(19A)-C(18A)-C(23A) C(19A)-C(18A)-C(17) 114.8(4) C(23A)-C(18A)-C(17) 125.0(4) C(18A)-C(19A)-C(20A) C(21A)-C(20A)-C(19A) C(20A)-C(21A)-C(22A) C(23A)-C(22A)-C(21A) C(22A)-C(23A)-C(18A) C(17)-C(24)-C(25) 121.3(9) N(2)-C(25)-C(24) 121.5(9) N(2)-C(25)-C(26) 117.7(9) C(24)-C(25)-C(26) 120.9(9) N(3)-C(27)-C(28) 121.3(11) N(3)-C(27)-Pd(1) 117.8(7) C(28)-C(27)-Pd(1) 71.0(6) C(27)-C(28)-C(29) 124.2(9) C(27)-C(28)-Pd(1) 68.4(6) C(29)-C(28)-Pd(1) 120.0(6) C(30)-C(29)-C(34) C(30)-C(29)-C(28) 117.6(7) C(34)-C(29)-C(28) 122.4(7) C(29)-C(30)-C(31) C(30)-C(31)-C(32) C(31)-C(32)-C(33) C(34)-C(33)-C(32) C(33)-C(34)-C(29) Cl(1)-C(35)-Cl(1)# (15) Symmetry transformations used to generate equivalent atoms: #1 -x+1,-y,-z 11

12 Table S4. Anisotropic displacement parameters (Å 2 x 10 3 ) for (bc)pd(ns H ). The anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 Pd(1) 43(1) 34(1) 48(1) 7(1) -4(1) -7(1) Cl(1) 141(4) 115(4) 224(6) -16(4) 17(4) 31(3) O(1) 116(8) 136(9) 59(6) 30(6) 31(5) 38(7) O(2) 64(6) 82(7) 135(9) 28(6) 17(6) -9(5) N(1) 59(6) 27(5) 44(5) 4(4) 2(4) -1(4) N(2) 43(5) 28(5) 40(5) 2(4) -2(4) 0(4) N(3) 103(10) 73(9) 41(6) 22(6) 17(6) 9(7) C(1) 207(17) 32(7) 73(9) 10(7) 42(10) 17(9) C(2) 97(10) 36(7) 48(7) -1(6) 4(6) 6(6) C(3) 78(8) 36(8) 60(7) -5(6) 14(6) 15(6) C(4) 47(7) 39(7) 45(6) 0(5) -2(5) 1(5) C(5) 54(7) 31(6) 47(6) -6(5) -1(5) 0(5) C(6) 40(7) 64(8) 60(7) -23(6) -1(6) 7(6) C(7) 57(8) 50(8) 80(9) -21(7) 12(7) 1(6) C(8) 82(10) 50(8) 65(8) -22(6) 37(7) -3(7) C(9) 90(10) 34(7) 43(7) -11(5) 0(6) -4(6) C(10) 43(7) 44(7) 59(7) -9(6) 5(6) -3(5) C(11) 48(6) 32(6) 42(6) -6(5) 2(5) 13(5) C(12) 41(6) 33(6) 52(6) 6(5) 1(5) 4(5) C(13) 59(7) 20(6) 59(7) 7(5) 1(5) 3(5) C(14) 46(7) 36(6) 37(6) 8(5) 1(5) -2(5) C(15) 21(5) 39(6) 37(5) 12(5) -3(4) 1(4) C(16) 43(6) 28(6) 41(6) 4(5) -5(5) -2(5) C(17) 41(6) 33(6) 46(6) 1(5) 1(5) 6(5) C(18) 68(4) 40(3) 53(4) 4(3) -17(3) 11(3) C(19) 68(4) 40(3) 53(4) 4(3) -17(3) 11(3) C(20) 68(4) 40(3) 53(4) 4(3) -17(3) 11(3) C(21) 68(4) 40(3) 53(4) 4(3) -17(3) 11(3) C(22) 68(4) 40(3) 53(4) 4(3) -17(3) 11(3) C(23) 68(4) 40(3) 53(4) 4(3) -17(3) 11(3) C(18A) 68(4) 40(3) 53(4) 4(3) -17(3) 11(3) C(19A) 68(4) 40(3) 53(4) 4(3) -17(3) 11(3) C(20A) 68(4) 40(3) 53(4) 4(3) -17(3) 11(3) C(21A) 68(4) 40(3) 53(4) 4(3) -17(3) 11(3) C(22A) 68(4) 40(3) 53(4) 4(3) -17(3) 11(3) C(23A) 68(4) 40(3) 53(4) 4(3) -17(3) 11(3) C(24) 36(6) 49(7) 49(6) 1(5) 2(5) 11(5) C(25) 36(6) 50(7) 37(6) 1(5) -6(5) -8(5) C(26) 44(7) 62(8) 52(7) 11(6) 9(5) -5(6) C(27) 48(7) 69(8) 44(6) 20(6) 5(5) -3(6) C(28) 46(7) 43(7) 52(7) 21(5) -3(5) -10(5) C(29) 41(7) 40(7) 60(7) 16(5) 0(5) -3(5) C(30) 54(8) 54(8) 81(9) 11(7) 19(6) 2(6) C(31) 62(9) 78(10) 130(13) 44(9) 21(9) 20(8) C(32) 60(10) 97(13) 132(14) 59(11) 6(9) 20(9) C(33) 78(11) 72(11) 120(12) 28(9) -5(9) -15(8) C(34) 58(8) 43(7) 105(10) 14(7) 4(7) -6(7) C(35) 100(20) 220(40) 120(30) -90(30) 50(20) 20(20) 12

13 Table S5. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for (bc)pd(ns H ). x y z U(eq) H(1A) H(1B) H(1C) H(3) H(6) H(7) H(8) H(9) H(10) H(12) H(13) H(19) H(20) H(21) H(22) H(23) H(19A) H(20A) H(21A) H(22A) H(23A) H(24) H(26A) H(26B) H(26C) H(27) H(28) H(30) H(31) H(32) H(33) H(34) H(35A) H(35B)

14 (bc)pd(ns CH3 ): Data Collection A yellow air-sensitive crystal with approximate dimensions 0.4 x 0.3 x 0.2 mm 3 was selected under oil under ambient conditions and attached to the tip of a glass capillary. The crystal was mounted in a stream of cold nitrogen at 173(2) K and centered in the X-ray beam by using a video camera. The crystal evaluation and data collection were performed on a Bruker CCD-1000 diffractometer with Mo Kα (λ = Å) radiation and the diffractometer to crystal distance of 4.9 cm. The initial cell constants were obtained from three series of ω scans at different starting angles. Each series consisted of 20 frames collected at intervals of 0.3º in a 6º range about ω with the exposure time of 10 seconds per frame. A total of 44 reflections was obtained. The reflections were successfully indexed by an automated indexing routine built in the SMART program. The final cell constants were calculated from a set of 7790 strong reflections from the actual data collection. The data were collected by using the hemisphere data collection routine. The reciprocal space was surveyed to the extent of a full sphere to a resolution of 0.80 Å. A total of data were harvested by collecting three sets of frames with 0.3º scans in ω with an exposure time 90 sec per frame. These highly redundant datasets were corrected for Lorentz and polarization effects. The absorption correction was based on fitting a function to the empirical transmission surface as sampled by multiple equivalent measurements. 2 Structure Solution and Refinement The systematic absences in the diffraction data were consistent for the space groups P1 and P1. 3 The E- statistics strongly suggested the centrosymmetric space group P1 that yielded chemically reasonable and computationally stable results of refinement. A successful solution by the direct methods provided most non-hydrogen atoms from the E-map. The remaining non-hydrogen atoms were located in an alternating series of least-squares cycles and difference Fourier maps. All non-hydrogen atoms were refined with anisotropic displacement coefficients. All hydrogen atoms were included in the structure factor calculation at idealized positions and were allowed to ride on the neighboring atoms with relative isotropic displacement coefficients. There are two symmetry independent molecules of the complex in the lattice. There was one solvate molecule present in the asymmetric unit. A significant amount of time was invested in identifying and refining the disordered molecule. Bond length restraints were applied to model that molecule but the resulting isotropic displacement coefficients suggested the molecules were mobile. In addition, the refinement was computationally unstable. Option SQUEEZE of program PLATON [3] was used to correct the diffraction data for diffuse scattering effects and to identify the solvate molecule. PLATON calculated the upper limit of volume that can be occupied by the solvent to be Å 3, or 10.7% of the unit cell volume. The program calculated 57 electrons in the unit cell for the diffuse species. This roughly corresponds to 1.35 molecules of diethyl ether per two molecules of the Pd complex. Please note that all derived results in the following tables are based on known contents. No data are given for the diffusely scattering species. The final least-squares refinement of 745 parameters against 9373 data resulted in residuals R (based on F 2 for 14

15 I 2σ) and wr (based on F 2 for all data) of and , respectively. The ORTEP diagrams are drawn with 30% probability ellipsoids. 15

16 Figure S2. ORTEP drawing of the p-methyl-β-nitrostyrene adduct of bathocuproine-coordinated palladium(0), (bc)pd(ns CH3 ). 16

17 Table S6. Crystal data and structure refinement for sta04. Identification code sta04 Empirical formula C 35 H 29 N 3 O 2 Pd. solvent Formula weight Temperature 173(2) K Wavelength Å Crystal system Triclinic Space group P1 Unit cell dimensions a = (15) Å a= (2). b = (15) Å b= (2). c = (17) Å g = (2). Volume (5) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1288 Crystal size 0.18 x 0.12 x 0.05 mm 3 Theta range for data collection 1.31 to Index ranges -16<=h<=16, -15<=k<=17, 0<=l<=19 Reflections collected Independent reflections 9373 [R(int) = ] Completeness to theta = % Absorption correction Empirical with SADABS Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 9373 / 0 / 745 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 17

18 Table S7. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for (bc)pd(ns CH3 ). U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) Pd(1) 7622(1) 8116(1) 4737(1) 31(1) Pd(2) 6334(1) 1287(1) 322(1) 29(1) O(1) 8794(5) 6521(6) 6955(4) 65(2) O(2) 8881(4) 8068(5) 6249(4) 52(2) O(1A) 6978(6) 2810(6) 995(4) 64(2) O(2A) 8499(5) 1737(6) 709(5) 78(2) N(1) 6143(5) 8086(5) 5082(4) 28(2) N(2) 6589(5) 9499(5) 3721(4) 28(2) N(3) 8876(5) 7223(7) 6277(5) 47(2) N(1A) 6949(5) -422(5) 1218(4) 31(2) N(2A) 5037(5) 934(5) 513(4) 27(2) N(3A) 7566(7) 2253(7) 581(5) 51(2) C(1) 6842(6) 6359(7) 6317(5) 43(2) C(2) 5935(6) 7340(6) 5741(5) 30(2) C(3) 4952(6) 7412(7) 5902(5) 35(2) C(4) 4119(6) 8297(7) 5387(5) 32(2) C(5) 4307(6) 9141(6) 4706(5) 28(2) C(6) 3495(6) 10173(6) 4199(5) 29(2) C(7) 3717(6) 10909(6) 3546(5) 28(2) C(8) 4765(6) 10718(6) 3312(5) 26(2) C(9) 5044(6) 11450(6) 2585(5) 27(2) C(10) 6076(6) 11162(7) 2467(5) 32(2) C(11) 6822(6) 10201(6) 3038(5) 28(2) C(12) 7961(5) 9914(7) 2893(5) 39(2) C(13) 5332(5) 8967(6) 4572(5) 23(2) C(14) 5562(6) 9758(6) 3844(5) 25(2) C(15) 3069(6) 8341(7) 5543(6) 40(2) C(16) 2448(7) 8628(7) 4866(6) 50(3) C(17) 1500(8) 8649(8) 5021(8) 66(3) C(18) 1148(8) 8383(9) 5854(9) 72(4) C(19) 1744(8) 8080(8) 6518(8) 64(3) C(20) 2695(7) 8063(7) 6360(6) 43(2) C(21) 4298(6) 12486(6) 1971(5) 29(2) C(22) 4455(6) 13418(7) 1656(5) 36(2) C(23) 3788(7) 14398(7) 1052(5) 41(2) C(24) 2948(7) 14484(7) 739(6) 51(3) C(25) 2780(6) 13564(7) 1024(6) 46(2) C(26) 3440(6) 12578(7) 1641(5) 37(2) C(27) 8930(6) 7031(7) 5485(5) 35(2) C(28) 9175(6) 7753(7) 4718(5) 37(2) C(29) 9802(6) 7300(7) 4051(5) 35(2) C(30) 9871(6) 6379(7) 3956(6) 43(2) C(31) 10489(7) 5999(8) 3318(6) 55(3) C(32) 11021(6) 6530(7) 2756(5) 38(2) C(33) 10973(6) 7440(8) 2841(6) 46(2) C(34) 10378(7) 7813(7) 3490(6) 48(2) C(35) 11590(7) 6151(8) 2035(6) 63(3) C(1A) 8771(6) -860(7) 1078(6) 47(2) 18

19 C(2A) 7920(6) -1157(7) 1479(5) 34(2) C(3A) 8149(6) -2192(7) 2123(5) 39(2) C(4A) 7387(6) -2494(6) 2551(5) 31(2) C(5A) 6349(6) -1703(6) 2294(5) 28(2) C(6A) 5489(6) -1909(7) 2669(5) 36(2) C(7A) 4519(6) -1192(6) 2346(5) 35(2) C(8A) 4325(5) -220(6) 1605(5) 25(2) C(9A) 3351(6) 481(6) 1180(5) 26(2) C(10A) 3288(6) 1310(6) 420(5) 30(2) C(11A) 4124(6) 1544(6) 106(5) 30(2) C(12A) 4003(6) 2532(6) -693(5) 37(2) C(13A) 6178(6) -726(6) 1611(5) 25(2) C(14A) 5144(6) 36(6) 1237(5) 26(2) C(15A) 7663(6) -3620(7) 3202(6) 39(2) C(16A) 8269(7) -4512(8) 2944(7) 63(3) C(17A) 8520(8) -5570(8) 3521(8) 73(3) C(18A) 8203(7) -5752(8) 4371(7) 57(3) C(19A) 7698(9) -4909(8) 4625(7) 69(3) C(20A) 7412(8) -3814(8) 4031(6) 58(3) C(21A) 2397(6) 359(6) 1540(5) 30(2) C(22A) 1862(6) 183(7) 1082(6) 40(2) C(23A) 926(7) 174(8) 1363(6) 48(3) C(24A) 544(7) 328(8) 2120(6) 52(3) C(25A) 1065(7) 492(8) 2590(6) 54(3) C(26A) 2007(7) 498(8) 2306(6) 51(3) C(27A) 7162(7) 2174(7) -100(6) 39(2) C(28A) 6108(6) 2884(6) -374(5) 32(2) C(29A) 5812(7) 3396(7) -1295(5) 41(2) C(30A) 6355(7) 2944(8) -1893(6) 47(2) C(31A) 6015(10) 3463(10) -2738(7) 70(3) C(32A) 5107(12) 4431(11) -3008(7) 75(4) C(33A) 4546(9) 4884(9) -2419(7) 68(3) C(34A) 4901(7) 4388(8) -1576(6) 50(3) C(35A) 4738(12) 4935(11) -3938(7) 125(6) 19

20 Table S8. Bond lengths [Å] and angles [ ] for (bc)pd(ns CH3 ). Pd(1)-C(27) 2.045(8) C(24)-C(25) 1.385(12) Pd(1)-C(28) 2.087(8) C(25)-C(26) 1.397(11) Pd(1)-N(2) 2.145(6) C(27)-C(28) 1.436(11) Pd(1)-N(1) 2.175(6) C(28)-C(29) 1.498(11) Pd(2)-C(27A) 2.057(8) C(29)-C(30) 1.400(11) Pd(2)-C(28A) 2.066(8) C(29)-C(34) 1.401(11) Pd(2)-N(2A) 2.159(6) C(30)-C(31) 1.408(11) Pd(2)-N(1A) 2.182(6) C(31)-C(32) 1.368(11) O(1)-N(3) 1.238(8) C(32)-C(33) 1.387(12) O(2)-N(3) 1.244(9) C(32)-C(35) 1.507(11) O(1A)-N(3A) 1.226(9) C(33)-C(34) 1.408(12) O(2A)-N(3A) 1.220(9) C(1A)-C(2A) 1.491(10) N(1)-C(2) 1.337(9) C(2A)-C(3A) 1.398(11) N(1)-C(13) 1.360(9) C(3A)-C(4A) 1.389(11) N(2)-C(11) 1.335(9) C(4A)-C(5A) 1.420(10) N(2)-C(14) 1.373(9) C(4A)-C(15A) 1.486(11) N(3)-C(27) 1.469(11) C(5A)-C(13A) 1.385(10) N(1A)-C(2A) 1.334(9) C(5A)-C(6A) 1.428(10) N(1A)-C(13A) 1.389(9) C(6A)-C(7A) 1.353(10) N(2A)-C(11A) 1.332(9) C(7A)-C(8A) 1.423(10) N(2A)-C(14A) 1.366(9) C(8A)-C(14A) 1.406(10) N(3A)-C(27A) 1.463(11) C(8A)-C(9A) 1.414(10) C(1)-C(2) 1.523(10) C(9A)-C(10A) 1.359(10) C(2)-C(3) 1.388(10) C(9A)-C(21A) 1.498(10) C(3)-C(4) 1.382(11) C(10A)-C(11A) 1.399(10) C(4)-C(5) 1.429(10) C(11A)-C(12A) 1.504(10) C(4)-C(15) 1.501(11) C(13A)-C(14A) 1.457(10) C(5)-C(13) 1.399(10) C(15A)-C(20A) 1.342(12) C(5)-C(6) 1.439(10) C(15A)-C(16A) 1.395(12) C(6)-C(7) 1.332(10) C(16A)-C(17A) 1.379(13) C(7)-C(8) 1.444(10) C(17A)-C(18A) 1.397(14) C(8)-C(14) 1.401(10) C(18A)-C(19A) 1.320(13) C(8)-C(9) 1.432(10) C(19A)-C(20A) 1.419(12) C(9)-C(10) 1.372(10) C(21A)-C(22A) 1.376(11) C(9)-C(21) 1.469(10) C(21A)-C(26A) 1.382(11) C(10)-C(11) 1.395(10) C(22A)-C(23A) 1.385(11) C(11)-C(12) 1.523(10) C(23A)-C(24A) 1.374(12) C(13)-C(14) 1.447(10) C(24A)-C(25A) 1.359(12) C(15)-C(20) 1.376(11) C(25A)-C(26A) 1.393(11) C(15)-C(16) 1.398(12) C(27A)-C(28A) 1.428(11) C(16)-C(17) 1.364(12) C(28A)-C(29A) 1.479(11) C(17)-C(18) 1.387(15) C(29A)-C(30A) 1.370(12) C(18)-C(19) 1.348(15) C(29A)-C(34A) 1.403(12) C(19)-C(20) 1.372(12) C(30A)-C(31A) 1.382(13) C(21)-C(22) 1.390(10) C(31A)-C(32A) 1.383(15) C(21)-C(26) 1.402(10) C(32A)-C(33A) 1.364(15) C(22)-C(23) 1.387(11) C(32A)-C(35A) 1.523(14) C(23)-C(24) 1.367(12) C(33A)-C(34A) 1.386(13) 20

21 C(27)-Pd(1)-C(28) 40.7(3) C(27)-Pd(1)-N(2) 160.4(3) C(28)-Pd(1)-N(2) 120.0(3) C(27)-Pd(1)-N(1) 123.4(3) C(28)-Pd(1)-N(1) 164.0(3) N(2)-Pd(1)-N(1) 76.0(2) C(27A)-Pd(2)-C(28A) 40.5(3) C(27A)-Pd(2)-N(2A) 159.3(3) C(28A)-Pd(2)-N(2A) 118.8(3) C(27A)-Pd(2)-N(1A) 123.8(3) C(28A)-Pd(2)-N(1A) 163.1(3) N(2A)-Pd(2)-N(1A) 76.7(2) C(2)-N(1)-C(13) 117.0(6) C(2)-N(1)-Pd(1) 128.3(5) C(13)-N(1)-Pd(1) 114.7(5) C(11)-N(2)-C(14) 116.8(6) C(11)-N(2)-Pd(1) 127.1(5) C(14)-N(2)-Pd(1) 115.7(5) O(1)-N(3)-O(2) 122.9(8) O(1)-N(3)-C(27) 116.5(8) O(2)-N(3)-C(27) 120.6(8) C(2A)-N(1A)-C(13A) 117.4(7) C(2A)-N(1A)-Pd(2) 129.8(5) C(13A)-N(1A)-Pd(2) 112.6(5) C(11A)-N(2A)-C(14A) 117.3(6) C(11A)-N(2A)-Pd(2) 129.1(5) C(14A)-N(2A)-Pd(2) 112.8(5) O(2A)-N(3A)-O(1A) 123.1(9) O(2A)-N(3A)-C(27A) 116.6(9) O(1A)-N(3A)-C(27A) 120.3(8) N(1)-C(2)-C(3) 123.2(7) N(1)-C(2)-C(1) 116.9(7) C(3)-C(2)-C(1) 119.9(7) C(4)-C(3)-C(2) 120.7(8) C(3)-C(4)-C(5) 117.5(7) C(3)-C(4)-C(15) 120.2(7) C(5)-C(4)-C(15) 122.3(7) C(13)-C(5)-C(4) 117.4(7) C(13)-C(5)-C(6) 119.3(7) C(4)-C(5)-C(6) 123.2(7) C(7)-C(6)-C(5) 120.6(7) C(6)-C(7)-C(8) 122.4(7) C(14)-C(8)-C(9) 118.0(7) C(14)-C(8)-C(7) 117.6(7) C(9)-C(8)-C(7) 124.5(7) C(10)-C(9)-C(8) 117.2(7) C(10)-C(9)-C(21) 118.6(7) C(8)-C(9)-C(21) 124.2(7) C(9)-C(10)-C(11) 121.3(7) N(2)-C(11)-C(10) 123.0(7) N(2)-C(11)-C(12) 117.0(7) C(10)-C(11)-C(12) 119.9(7) N(1)-C(13)-C(5) 124.1(7) N(1)-C(13)-C(14) 117.0(6) 21

22 C(5)-C(13)-C(14) 118.9(7) N(2)-C(14)-C(8) 123.7(7) N(2)-C(14)-C(13) 115.7(6) C(8)-C(14)-C(13) 120.6(7) C(20)-C(15)-C(16) 117.4(8) C(20)-C(15)-C(4) 121.3(8) C(16)-C(15)-C(4) 121.3(8) C(17)-C(16)-C(15) 120.5(10) C(16)-C(17)-C(18) 119.9(11) C(19)-C(18)-C(17) 120.5(10) C(18)-C(19)-C(20) 119.4(11) C(19)-C(20)-C(15) 122.1(10) C(22)-C(21)-C(26) 116.8(7) C(22)-C(21)-C(9) 120.1(7) C(26)-C(21)-C(9) 123.0(7) C(23)-C(22)-C(21) 121.7(8) C(24)-C(23)-C(22) 121.1(8) C(23)-C(24)-C(25) 118.9(9) C(24)-C(25)-C(26) 120.3(9) C(25)-C(26)-C(21) 121.2(8) C(28)-C(27)-N(3) 116.4(8) C(28)-C(27)-Pd(1) 71.2(4) N(3)-C(27)-Pd(1) 112.4(5) C(27)-C(28)-C(29) 118.6(7) C(27)-C(28)-Pd(1) 68.1(4) C(29)-C(28)-Pd(1) 115.2(6) C(30)-C(29)-C(34) 117.1(8) C(30)-C(29)-C(28) 124.4(8) C(34)-C(29)-C(28) 118.5(8) C(29)-C(30)-C(31) 120.8(8) C(32)-C(31)-C(30) 121.5(9) C(31)-C(32)-C(33) 118.8(8) C(31)-C(32)-C(35) 119.2(9) C(33)-C(32)-C(35) 121.9(8) C(32)-C(33)-C(34) 120.3(8) C(29)-C(34)-C(33) 121.5(8) N(1A)-C(2A)-C(3A) 121.1(7) N(1A)-C(2A)-C(1A) 119.0(7) C(3A)-C(2A)-C(1A) 119.8(7) C(4A)-C(3A)-C(2A) 122.4(7) C(3A)-C(4A)-C(5A) 116.8(7) C(3A)-C(4A)-C(15A) 120.8(7) C(5A)-C(4A)-C(15A) 122.3(7) C(13A)-C(5A)-C(4A) 117.9(7) C(13A)-C(5A)-C(6A) 119.1(7) C(4A)-C(5A)-C(6A) 122.8(7) C(7A)-C(6A)-C(5A) 121.4(8) C(6A)-C(7A)-C(8A) 120.9(7) C(14A)-C(8A)-C(9A) 117.4(7) C(14A)-C(8A)-C(7A) 119.5(7) C(9A)-C(8A)-C(7A) 123.0(7) C(10A)-C(9A)-C(8A) 117.8(7) C(10A)-C(9A)-C(21A) 119.4(7) C(8A)-C(9A)-C(21A) 122.8(7) 22

23 C(9A)-C(10A)-C(11A) 121.6(7) N(2A)-C(11A)-C(10A) 121.9(7) N(2A)-C(11A)-C(12A) 117.5(7) C(10A)-C(11A)-C(12A) 120.6(7) C(5A)-C(13A)-N(1A) 124.1(7) C(5A)-C(13A)-C(14A) 120.0(7) N(1A)-C(13A)-C(14A) 115.9(7) N(2A)-C(14A)-C(8A) 123.6(7) N(2A)-C(14A)-C(13A) 117.5(7) C(8A)-C(14A)-C(13A) 118.8(7) C(20A)-C(15A)-C(16A) 119.1(9) C(20A)-C(15A)-C(4A) 122.9(8) C(16A)-C(15A)-C(4A) 117.8(8) C(17A)-C(16A)-C(15A) 119.8(10) C(16A)-C(17A)-C(18A) 120.1(10) C(19A)-C(18A)-C(17A) 119.5(10) C(18A)-C(19A)-C(20A) 120.8(10) C(15A)-C(20A)-C(19A) 120.4(9) C(22A)-C(21A)-C(26A) 119.4(7) C(22A)-C(21A)-C(9A) 120.0(7) C(26A)-C(21A)-C(9A) 120.5(7) C(21A)-C(22A)-C(23A) 120.9(8) C(24A)-C(23A)-C(22A) 118.8(8) C(25A)-C(24A)-C(23A) 121.3(8) C(24A)-C(25A)-C(26A) 119.8(9) C(21A)-C(26A)-C(25A) 119.7(8) C(28A)-C(27A)-N(3A) 119.6(8) C(28A)-C(27A)-Pd(2) 70.1(4) N(3A)-C(27A)-Pd(2) 114.8(5) C(27A)-C(28A)-C(29A) 120.9(8) C(27A)-C(28A)-Pd(2) 69.4(4) C(29A)-C(28A)-Pd(2) 119.6(6) C(30A)-C(29A)-C(34A) 117.2(9) C(30A)-C(29A)-C(28A) 124.2(9) C(34A)-C(29A)-C(28A) 118.6(9) C(29A)-C(30A)-C(31A) 120.6(10) C(30A)-C(31A)-C(32A) 121.8(11) C(33A)-C(32A)-C(31A) 118.5(11) C(33A)-C(32A)-C(35A) 121.9(13) C(31A)-C(32A)-C(35A) 119.6(14) C(32A)-C(33A)-C(34A) 120.0(11) C(33A)-C(34A)-C(29A) 121.8(10) Symmetry transformations used to generate equivalent atoms: 23

24 Table S9. Anisotropic displacement parameters (Å 2 x 10 3 ) for sta04. The anisotropic displacement factor exponent takes the form: -2p 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 Pd(1) 23(1) 32(1) 36(1) -13(1) 1(1) -10(1) Pd(2) 26(1) 31(1) 32(1) -10(1) 4(1) -17(1) O(1) 70(5) 69(5) 45(4) -10(4) 4(4) -35(4) O(2) 43(4) 57(4) 65(5) -34(4) -3(3) -18(3) O(1A) 76(5) 84(6) 58(5) -28(4) 6(4) -56(5) O(2A) 49(5) 75(5) 109(6) -15(5) -25(4) -34(4) N(1) 30(4) 22(4) 35(4) -17(3) 7(3) -12(3) N(2) 26(4) 27(4) 30(4) -11(3) 3(3) -13(3) N(3) 27(4) 45(5) 47(5) -7(5) 7(4) -11(4) N(1A) 26(4) 33(4) 37(4) -20(3) 1(3) -9(3) N(2A) 28(4) 23(4) 33(4) -14(3) 0(3) -9(3) N(3A) 44(5) 55(6) 58(6) 3(5) -1(4) -44(5) C(1) 44(6) 37(5) 34(5) 0(4) -1(4) -18(5) C(2) 31(5) 31(5) 39(5) -19(4) 4(4) -18(4) C(3) 45(5) 35(5) 28(5) -10(4) 10(4) -24(5) C(4) 37(5) 35(5) 34(5) -19(4) 9(4) -23(4) C(5) 27(5) 38(5) 26(5) -19(4) 8(4) -17(4) C(6) 19(4) 38(5) 37(5) -19(4) 5(4) -15(4) C(7) 21(4) 33(5) 38(5) -21(4) 4(4) -13(4) C(8) 26(4) 33(5) 27(5) -20(4) 6(4) -14(4) C(9) 27(5) 25(4) 32(5) -16(4) -2(4) -9(4) C(10) 35(5) 40(5) 28(5) -14(4) 4(4) -21(4) C(11) 20(4) 32(5) 35(5) -18(4) 4(4) -11(4) C(12) 20(4) 43(5) 47(6) -17(5) 7(4) -10(4) C(13) 17(4) 21(4) 31(5) -14(4) 2(3) -5(3) C(14) 22(4) 25(4) 31(5) -13(4) 4(4) -12(4) C(15) 32(5) 34(5) 58(6) -17(5) 15(5) -21(4) C(16) 48(6) 58(6) 54(6) -14(5) -1(5) -36(5) C(17) 43(6) 60(7) 104(10) -34(7) 3(6) -30(6) C(18) 40(7) 62(8) 130(12) -43(8) 28(7) -36(6) C(19) 56(7) 57(7) 93(9) -45(7) 45(7) -38(6) C(20) 49(6) 37(5) 54(6) -21(5) 17(5) -30(5) C(21) 29(5) 26(5) 33(5) -14(4) 5(4) -11(4) C(22) 35(5) 42(6) 31(5) -14(5) 3(4) -17(4) C(23) 40(6) 35(5) 45(6) -11(5) 5(5) -19(5) C(24) 52(6) 32(6) 50(6) -14(5) -4(5) -4(5) C(25) 32(5) 48(6) 50(6) -22(5) -12(5) -5(5) C(26) 42(5) 38(5) 36(5) -23(5) 6(4) -17(4) C(27) 26(5) 39(5) 34(5) -18(4) 5(4) -8(4) C(28) 21(4) 37(5) 43(6) -10(5) 0(4) -8(4) C(29) 25(5) 37(5) 33(5) -10(4) 6(4) -10(4) C(30) 36(5) 33(5) 47(6) -12(5) 3(4) -10(4) C(31) 50(6) 41(6) 49(6) -8(5) -1(5) -9(5) C(32) 23(5) 43(6) 37(6) -7(5) 7(4) -15(4) C(33) 38(5) 54(6) 43(6) -14(5) 14(5) -26(5) C(34) 41(6) 47(6) 54(6) -12(5) 1(5) -24(5) C(35) 52(6) 71(7) 53(7) -26(6) 16(5) -21(6) C(1A) 24(5) 54(6) 56(6) -15(5) 6(4) -20(5) 24

25 C(2A) 24(5) 41(5) 38(5) -15(5) -3(4) -16(4) C(3A) 23(5) 39(5) 46(6) -15(5) -7(4) -5(4) C(4A) 33(5) 34(5) 33(5) -16(4) -4(4) -15(4) C(5A) 26(4) 24(4) 36(5) -12(4) -5(4) -11(4) C(6A) 49(6) 29(5) 31(5) -9(4) 1(4) -19(4) C(7A) 24(5) 33(5) 43(5) -10(4) 7(4) -15(4) C(8A) 20(4) 26(4) 32(5) -13(4) 6(4) -12(4) C(9A) 24(4) 29(5) 31(5) -15(4) 0(4) -14(4) C(10A) 22(4) 34(5) 37(5) -16(4) -1(4) -12(4) C(11A) 28(5) 33(5) 32(5) -17(4) 2(4) -13(4) C(12A) 29(5) 39(5) 34(5) 0(4) -5(4) -19(4) C(13A) 25(4) 16(4) 36(5) -14(4) 1(4) -6(4) C(14A) 26(4) 23(4) 33(5) -12(4) -2(4) -11(4) C(15A) 30(5) 36(5) 42(6) -10(5) -1(4) -10(4) C(16A) 55(7) 51(7) 63(7) -17(6) -1(6) -12(6) C(17A) 78(8) 34(6) 80(9) -9(6) -8(7) -12(6) C(18A) 55(7) 22(5) 77(8) 4(6) -30(6) -14(5) C(19A) 96(9) 43(7) 46(7) 1(6) -16(6) -25(6) C(20A) 79(8) 36(6) 58(7) -21(6) -2(6) -21(5) C(21A) 25(4) 32(5) 38(5) -14(4) 10(4) -20(4) C(22A) 39(5) 46(6) 45(6) -22(5) 9(4) -26(5) C(23A) 33(5) 68(7) 58(7) -32(6) -4(5) -24(5) C(24A) 32(5) 60(7) 62(7) -18(6) 9(5) -27(5) C(25A) 41(6) 85(8) 52(6) -37(6) 13(5) -35(6) C(26A) 53(6) 87(8) 45(6) -34(6) 22(5) -54(6) C(27A) 42(5) 47(6) 41(5) -15(5) 6(4) -33(5) C(28A) 38(5) 29(5) 34(5) -9(4) -1(4) -19(4) C(29A) 54(6) 43(6) 35(6) 0(5) 0(5) -41(5) C(30A) 55(6) 61(7) 32(6) -13(5) 10(5) -37(5) C(31A) 118(11) 77(9) 50(7) -21(7) 15(7) -77(9) C(32A) 129(12) 74(9) 45(7) 10(7) -28(8) -79(9) C(33A) 93(9) 60(7) 55(8) 9(6) -25(7) -54(7) C(34A) 52(6) 52(6) 45(6) -4(5) -9(5) -33(5) C(35A) 243(19) 109(11) 54(8) 6(8) -52(10) -114(13) 25

26 Table S10. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for (bc)pd(ns CH3 ). x y z U(eq) H(1A) H(1B) H(1C) H(3) H(6) H(7) H(10) H(12A) H(12B) H(12C) H(16) H(17) H(18) H(19) H(20) H(22) H(23) H(24) H(25) H(26) H(27) H(28) H(30) H(31) H(33) H(34) H(35A) H(35B) H(35C) H(1A1) H(1A2) H(1A3) H(3A) H(6A) H(7A) H(10A) H(12D) H(12E) H(12F) H(16A) H(17A) H(18A) H(19A) H(20A) H(22A) H(23A) H(24A)

27 H(25A) H(26A) H(27A) H(28A) H(30A) H(31A) H(33A) H(34A) H(35D) H(35E) H(35F)

28 (bc)pd(ns Br ): Data collection. A red air- and moisture-sensitive crystal with approximate dimensions 0.30 x 0.20 x 0.10 mm 3 was selected under oil at ambient conditions and attached to the tip of a glass capillary. The crystal was mounted in a stream of cold nitrogen at 173(2) K and centered in the X-ray beam by using a video camera. The crystal evaluation and data collection were performed on a Bruker CCD-1000 diffractometer with Mo Kα (λ = Å) radiation and a diffractometer to crystal distance of cm. The initial cell constants were obtained from three series of ω scans at different starting angles. Each series consisted of 20 frames collected at intervals of 0.3º in a 6º range about ω with the exposure time of 10 seconds per frame. A total of 57 reflections was obtained. The reflections were successfully indexed by an automated indexing routine built in the SMART program. The final cell constants were calculated from a set of 7685 strong reflections from the actual data collection. The data were collected by using the multirun data collection routine. The reciprocal space was surveyed to the extent of a full sphere to a resolution of 0.80 Å. A total of data were harvested by collecting three sets of frames with 0.3º scans in ω with an exposure time 30 sec per frame. This highly redundant dataset was corrected for Lorentz and polarization effects. The absorption correction was based on fitting a function to the empirical transmission surface as sampled by multiple equivalent measurements. 2 Structure Solution and Refinement The systematic absences in the diffraction data were consistent for the space groups P1 and P1. 3 The E-statistics strongly suggested the centrosymmetric space group P1 that yielded chemically reasonable and computationally stable results of refinement. A successful solution by the direct methods provided most non-hydrogen atoms from the E-map. The remaining non-hydrogen atoms were located in an alternating series of 28

29 least-squares cycles and difference Fourier maps. All non-hydrogen atoms were refined with anisotropic displacement coefficients. All hydrogen atoms were included in the structure factor calculation at idealized positions and were allowed to ride on the neighboring atoms with relative isotropic displacement coefficients. There is one palladium complex and two solvate molecules of dichloromethane in the asymmetric unit. The final least-squares refinement of 426 parameters against 6935 data resulted in residuals R (based on F 2 for I 2σ) and wr (based on F 2 for all data) of and , respectively. The final difference Fourier map was featureless. The ORTEP diagrams are drawn with 30% probability ellipsoids. 29

30 Figure S3. ORTEP drawing of the p-methyl-β-nitrostyrene adduct of bathocuproine-coordinated palladium(0), (bc)pd(ns Br ). 30

31 Table S11. Crystal data and structure refinement for (bc)pd(ns Br ). Identification code sta03 Empirical formula C 36 H 30 Br Cl 4 N 3 O 2 Pd Formula weight Temperature 173(2) K Wavelength Å Crystal system Triclinic Space group P1 Unit cell dimensions a = (8) Å α= (1). b = (9) Å β= (1). c = (10) Å γ = (1). Volume (2) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 864 Crystal size 0.30 x 0.20 x 0.10 mm 3 Theta range for data collection 1.66 to Index ranges -12<=h<=13, -14<=k<=16, 0<=l<=17 Reflections collected Independent reflections 6935 [R(int) = ] Completeness to theta = % Absorption correction Empirical with SADABS Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 6935 / 0 / 426 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 31

32 Table S12. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for (bc)pd(ns Br ). U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) Pd 6947(1) 11031(1) 2186(1) 22(1) Br 5501(1) 16749(1) 1488(1) 50(1) Cl(1) 8107(1) 8103(1) 1897(1) 50(1) Cl(2) 9265(2) 8250(1) 3599(1) 54(1) Cl(3) 1073(2) 5636(2) 1701(2) 86(1) Cl(4) 2650(2) 4586(2) 3383(2) 73(1) O(1) 9054(3) 11132(3) 44(3) 42(1) O(2) 7527(4) 11413(3) -884(3) 46(1) N(1) 5722(3) 9584(3) 2984(3) 22(1) N(2) 7254(3) 10395(3) 3860(3) 23(1) N(3) 7973(4) 11470(3) -132(3) 32(1) C(1) 4985(4) 9191(4) 2514(3) 27(1) C(2) 4184(4) 8279(4) 3127(4) 27(1) C(3) 4133(4) 7719(4) 4234(3) 25(1) C(4) 4905(4) 8138(3) 4738(3) 23(1) C(5) 4891(4) 7681(4) 5895(3) 25(1) C(6) 5687(4) 8073(4) 6327(3) 24(1) C(7) 6577(4) 8955(3) 5666(3) 23(1) C(8) 7515(4) 9331(4) 6071(3) 25(1) C(9) 8246(4) 10236(4) 5352(3) 26(1) C(10) 8091(4) 10768(3) 4261(3) 24(1) C(11) 6520(4) 9494(3) 4547(3) 21(1) C(12) 5686(4) 9060(3) 4077(3) 22(1) C(13) 5045(5) 9760(4) 1310(4) 36(1) C(14) 3298(4) 6729(4) 4842(4) 26(1) C(15) 1997(5) 6798(4) 4752(4) 35(1) C(16) 1203(5) 5880(4) 5295(4) 41(1) C(17) 1712(5) 4866(5) 5913(4) 44(1) C(18) 2993(5) 4792(4) 5997(4) 41(1) C(19) 3781(5) 5715(4) 5481(4) 33(1) C(20) 7770(4) 8769(4) 7209(3) 26(1) C(21) 7869(4) 7616(4) 7711(4) 30(1) C(22) 8202(5) 7111(4) 8742(4) 35(1) C(23) 8444(5) 7738(4) 9280(4) 36(1) C(24) 8350(5) 8888(4) 8798(4) 35(1) C(25) 8018(4) 9402(4) 7758(4) 30(1) C(26) 8881(4) 11757(4) 3503(4) 31(1) C(27) 7174(4) 11970(4) 536(3) 28(1) C(28) 7808(4) 12488(4) 1059(3) 28(1) C(29) 7219(4) 13493(4) 1192(3) 28(1) C(30) 5940(4) 13779(4) 1132(3) 29(1) C(31) 5413(5) 14731(4) 1231(4) 35(1) C(32) 6195(5) 15413(4) 1406(4) 36(1) C(33) 7484(5) 15155(4) 1484(4) 34(1) C(34) 7976(4) 14208(4) 1377(4) 31(1) C(35) 9145(5) 8870(4) 2216(4) 41(1) C(36) 1920(7) 5807(6) 2607(7) 72(2) 32

33 Table S13. Bond lengths [Å] and angles [ ] for (bc)pd(ns Br ). Pd-C(28) 2.057(4) C(7)-C(8) 1.424(6) Pd-C(27) 2.060(4) C(8)-C(9) 1.376(6) Pd-N(1) 2.160(3) C(8)-C(20) 1.490(6) Pd-N(2) 2.169(3) C(9)-C(10) 1.399(6) Br-C(32) 1.897(5) C(10)-C(26) 1.489(6) Cl(1)-C(35) 1.764(5) C(11)-C(12) 1.447(6) Cl(2)-C(35) 1.750(6) C(14)-C(19) 1.387(7) Cl(3)-C(36) 1.744(8) C(14)-C(15) 1.396(6) Cl(4)-C(36) 1.743(8) C(15)-C(16) 1.383(7) O(1)-N(3) 1.225(5) C(16)-C(17) 1.390(8) O(2)-N(3) 1.235(5) C(17)-C(18) 1.372(8) N(1)-C(1) 1.341(5) C(18)-C(19) 1.383(7) N(1)-C(12) 1.360(5) C(20)-C(25) 1.394(6) N(2)-C(10) 1.335(5) C(20)-C(21) 1.396(6) N(2)-C(11) 1.363(5) C(21)-C(22) 1.389(6) N(3)-C(27) 1.453(6) C(22)-C(23) 1.372(7) C(1)-C(2) 1.391(6) C(23)-C(24) 1.390(7) C(1)-C(13) 1.494(6) C(24)-C(25) 1.400(6) C(2)-C(3) 1.379(6) C(27)-C(28) 1.437(6) C(3)-C(4) 1.422(6) C(28)-C(29) 1.488(6) C(3)-C(14) 1.482(6) C(29)-C(30) 1.385(6) C(4)-C(12) 1.400(6) C(29)-C(34) 1.404(6) C(4)-C(5) 1.442(6) C(30)-C(31) 1.384(7) C(5)-C(6) 1.347(6) C(31)-C(32) 1.380(7) C(6)-C(7) 1.433(6) C(32)-C(33) 1.393(7) C(7)-C(11) 1.410(6) C(33)-C(34) 1.372(7) 33

34 C(28)-Pd-C(27) 40.86(18) C(28)-Pd-N(1) (15) C(27)-Pd-N(1) (15) C(28)-Pd-N(2) (16) C(27)-Pd-N(2) (16) N(1)-Pd-N(2) 76.59(13) C(1)-N(1)-C(12) 118.4(4) C(1)-N(1)-Pd 126.5(3) C(12)-N(1)-Pd 115.0(3) C(10)-N(2)-C(11) 118.5(3) C(10)-N(2)-Pd 127.2(3) C(11)-N(2)-Pd 114.3(3) O(1)-N(3)-O(2) 121.8(4) O(1)-N(3)-C(27) 120.7(4) O(2)-N(3)-C(27) 117.6(4) N(1)-C(1)-C(2) 121.1(4) N(1)-C(1)-C(13) 118.1(4) C(2)-C(1)-C(13) 120.8(4) C(3)-C(2)-C(1) 122.1(4) C(2)-C(3)-C(4) 117.0(4) C(2)-C(3)-C(14) 119.9(4) C(4)-C(3)-C(14) 123.1(4) C(12)-C(4)-C(3) 118.1(4) C(12)-C(4)-C(5) 118.7(4) C(3)-C(4)-C(5) 123.2(4) C(6)-C(5)-C(4) 120.9(4) C(5)-C(6)-C(7) 121.9(4) C(11)-C(7)-C(8) 117.6(4) C(11)-C(7)-C(6) 118.4(4) C(8)-C(7)-C(6) 124.0(4) C(9)-C(8)-C(7) 117.4(4) C(9)-C(8)-C(20) 119.2(4) C(7)-C(8)-C(20) 123.4(4) C(8)-C(9)-C(10) 121.8(4) N(2)-C(10)-C(9) 121.3(4) N(2)-C(10)-C(26) 117.9(4) C(9)-C(10)-C(26) 120.8(4) N(2)-C(11)-C(7) 123.2(4) N(2)-C(11)-C(12) 117.3(3) C(7)-C(11)-C(12) 119.5(4) N(1)-C(12)-C(4) 123.2(4) N(1)-C(12)-C(11) 116.6(4) C(4)-C(12)-C(11) 120.2(4) C(19)-C(14)-C(15) 118.5(4) C(19)-C(14)-C(3) 121.7(4) C(15)-C(14)-C(3) 119.8(4) C(16)-C(15)-C(14) 120.9(5) C(15)-C(16)-C(17) 119.6(5) C(18)-C(17)-C(16) 119.7(5) C(17)-C(18)-C(19) 120.8(5) C(18)-C(19)-C(14) 120.4(4) C(25)-C(20)-C(21) 118.7(4) C(25)-C(20)-C(8) 119.8(4) C(21)-C(20)-C(8) 121.3(4) C(22)-C(21)-C(20) 120.6(4) C(23)-C(22)-C(21) 120.5(4) C(22)-C(23)-C(24) 120.1(4) C(23)-C(24)-C(25) 119.7(4) C(20)-C(25)-C(24) 120.5(4) C(28)-C(27)-N(3) 117.8(4) C(28)-C(27)-Pd 69.5(2) N(3)-C(27)-Pd 115.0(3) C(27)-C(28)-C(29) 118.8(4) C(27)-C(28)-Pd 69.7(2) C(29)-C(28)-Pd 113.5(3) C(30)-C(29)-C(34) 117.1(4) C(30)-C(29)-C(28) 123.2(4) C(34)-C(29)-C(28) 119.7(4) C(31)-C(30)-C(29) 122.6(4) C(32)-C(31)-C(30) 118.4(5) C(31)-C(32)-C(33) 121.2(5) C(31)-C(32)-Br 118.8(4) C(33)-C(32)-Br 120.0(4) C(34)-C(33)-C(32) 118.9(4) C(33)-C(34)-C(29) 121.9(4) Cl(2)-C(35)-Cl(1) 110.7(3) Cl(4)-C(36)-Cl(3) 112.8(4) Symmetry transformations used to generate equivalent atoms:

35 Table S14. Anisotropic displacement parameters (Å 2 x 10 3 ) for (bc)pd(ns Br ). The anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 Pd 25(1) 24(1) 17(1) -6(1) -4(1) 1(1) Br 53(1) 40(1) 67(1) -30(1) -19(1) 12(1) Cl(1) 52(1) 53(1) 53(1) -27(1) -13(1) -3(1) Cl(2) 54(1) 55(1) 56(1) -21(1) -24(1) 11(1) Cl(3) 109(2) 90(1) 56(1) -24(1) -14(1) -15(1) Cl(4) 81(1) 78(1) 71(1) -40(1) -12(1) 3(1) O(1) 38(2) 49(2) 38(2) -20(2) -6(2) 11(2) O(2) 56(2) 56(2) 35(2) -26(2) -12(2) -2(2) N(1) 24(2) 27(2) 17(2) -10(1) -5(1) 2(1) N(2) 24(2) 25(2) 20(2) -9(2) -4(1) 2(1) N(3) 38(2) 32(2) 25(2) -11(2) -2(2) -1(2) C(1) 26(2) 34(2) 23(2) -13(2) -7(2) 4(2) C(2) 23(2) 34(2) 29(2) -17(2) -6(2) -1(2) C(3) 25(2) 27(2) 26(2) -12(2) -6(2) 2(2) C(4) 21(2) 26(2) 24(2) -12(2) -5(2) 1(2) C(5) 23(2) 26(2) 19(2) -4(2) -1(2) -2(2) C(6) 25(2) 29(2) 15(2) -5(2) -3(2) 0(2) C(7) 24(2) 26(2) 20(2) -9(2) -5(2) 2(2) C(8) 28(2) 26(2) 22(2) -11(2) -7(2) 1(2) C(9) 28(2) 25(2) 26(2) -9(2) -10(2) 0(2) C(10) 25(2) 24(2) 24(2) -11(2) -3(2) 0(2) C(11) 23(2) 24(2) 18(2) -10(2) -4(2) 2(2) C(12) 22(2) 23(2) 20(2) -9(2) -4(2) 5(2) C(13) 37(3) 48(3) 21(2) -10(2) -7(2) -10(2) C(14) 27(2) 30(2) 29(2) -17(2) -6(2) -2(2) C(15) 31(2) 35(3) 41(3) -15(2) -13(2) 1(2) C(16) 28(3) 43(3) 55(3) -21(3) -9(2) -9(2) C(17) 47(3) 41(3) 42(3) -11(2) -5(2) -16(2) C(18) 51(3) 31(3) 37(3) -7(2) -12(2) -4(2) C(19) 31(2) 34(3) 31(2) -10(2) -6(2) -2(2) C(20) 24(2) 31(2) 23(2) -8(2) -7(2) -2(2) C(21) 34(2) 32(2) 26(2) -13(2) -8(2) -5(2) C(22) 42(3) 31(3) 26(2) -3(2) -9(2) -3(2) C(23) 41(3) 40(3) 22(2) -5(2) -11(2) -7(2) C(24) 38(3) 43(3) 32(3) -20(2) -11(2) -1(2) C(25) 33(2) 32(2) 27(2) -10(2) -10(2) -1(2) C(26) 30(2) 35(3) 27(2) -9(2) -5(2) -10(2) C(27) 32(2) 28(2) 20(2) -6(2) -3(2) 1(2) C(28) 29(2) 29(2) 22(2) -7(2) 0(2) -2(2) C(29) 34(2) 27(2) 17(2) -1(2) -3(2) -3(2) C(30) 33(2) 28(2) 24(2) -9(2) -3(2) -2(2) C(31) 36(3) 37(3) 30(2) -11(2) -9(2) 6(2) C(32) 44(3) 33(3) 33(3) -16(2) -7(2) 4(2) C(33) 40(3) 32(3) 31(2) -12(2) -7(2) -4(2) C(34) 29(2) 32(2) 29(2) -8(2) -6(2) -1(2) C(35) 40(3) 33(3) 51(3) -19(2) -6(2) -4(2) C(36) 64(4) 68(5) 90(5) -43(4) -2(4) -9(4)