SUPPORTING INFORMATION. Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives

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1 SUPPORTIG IFORMATIO Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd II Complexes Alexander S. Mikherdov, Mikhail A. Kinzhalov, Alexander S. ovikov, Vadim P. Boyarskiy, Irina A. Boyarskaya, Dmitry V. Dar'in, Galina L. Starova, Vadim Yu. Kukushkin Saint Petersburg State University, 7/9 Universitetskaya ab., Saint Petersburg , Russian Federation Table of Content Materials and Instrumentation... 2 Synthetic work... 2 Table S Regioisomer assignment by 2D MR spectroscopy... 7 Characterization data and MR spectra X-ray Structure Determinations Table S Table S Table S Table S References S1

2 Materials and Instrumentation Solvents, PdCl 2, heterocycles 1, 2, 6 9, and xylyl isocyanide were obtained from commercial sources and used as received, apart from chloroform, which was dried by the distillation over calcium chloride. Complex cis-[pdcl 2 (CXyl) 2 ] [1] and heterocycles 3 5 [2] were synthesized by the modified literature procedures. Melting points were determined in capillaries with a Stuart SMP 30 apparatus. C, H, and elemental analyses were carried out on a Euro EA 3028 HT CHSO analyzer. Mass-spectra were obtained on a Bruker microtof spectrometer equipped with electrospray ionization (ESI) source, a mixture of MeOH and CH 2 Cl 2 was used for samples dissolution. The instrument was operated at a positive ion mode using m/z range of The capillary voltage of the ion source was set at 4500 V and the capillary exit at V. The nebulizer gas pressure was 0.4 bar and the drying gas flow 4.0 L/min. The most intensive peak in the isotopic pattern is reported. Infrared spectra were recorded on a Perkin Elmer Spectrum BX FT-IR spectrometer ( cm 1 ) in KBr pellets for solid samples and in IR cells (KBr, l = 1.05 mm) for chloroform solutions. 1D ( 1 H, 13 C{ 1 H}) MR spectra were acquired on a Bruker Avance 400 spectrometer, while 2D ( 1 H, 1 H-COSY, 1 H, 1 H-OESY, 1 H, 13 C-HMQC/HSQC, and 1 H, 13 C-HMBC) MR correlation experiments were recorded on a Bruker Avance II+ 500 MHz (UltraShield Magnet) spectrometer. All MR spectra were acquired in CDCl 3 at ambient temperature. Synthetic work Synthesis of cis-[pdcl 2 (CXyl) 2 ]. [1] A solution of xylyl isocyanide (1.02 g, 7.70 mmol) in CHCl 3 (5 ml) was added dropwise at C to a suspension of cis-[pdcl 2 (MeC) 2 ] (1.00 g, 3.85 mmol, prepared by the literature procedure [3] ) in CHCl 3 (5 ml) placed in 25-mL round-bottom flask, and the reaction mixture was then refluxed for ca. 3 h. The reaction mixtures became gradually pale yellow and the product precipitated as a pale yellow powder. The formed precipitate was filtered off, washed with diethyl ether (three 1-mL portions), and dried in air at C. The mother liquor was concentrated at C to volume ca. 3 ml and Et 2 O (10 S2

3 ml) was added to the rest. The formed pale yellow solid was washed with Et 2 O, dried in air at C and combined with the first portion. Yield: 89% (1.50 g). HRESI + -MS: calcd for C 18 H 18 Cl 2 2 Pda , found m/z [M+a] +. IR (KBr, selected bands, cm 1 ): ν(c ) 2229 (s), 2212 (s). 1 H MR (δ, ppm, J/Hz): 2.50 (s, 12H, Me), 7.17 (d, 4H, J = 7.7), 7.33 (t, 2H, J = 7.7). 13 C{ 1 H} MR (δ, ppm): 18.85, , , , , Synthesis of heterocycles Chloro-thiazol-2-amine 3. [2] A solution of thiazol-2-amine 1 (0.50 mg, 5.0 mmol) in glacial acetic acid (10 ml) was added to solid -chlorosuccinimide (0.67 g, 5.0 mmol) placed in a 25- ml round-bottom flask and the reaction mixture was stirred in air at RT for 24 h. The solution was diluted with H 2 O (100 ml), adjusted to ph 7 with solid ahco 3, filtered off from some insoluble material and extracted with CH 2 Cl 2 (three 15-mL portions). Combined organic fractions were dried over a 2 SO 4 and concentrated on a rotary evaporator to give an orange solid. The crude product was purified by column chromatography (ethyl acetate/dichloromethane 1:2) to give a white solid. Yield: 31% (210 mg). M.p. = C. HRESI + -MS: calcd for C 3 H 4 Cl 2 S , found m/z [M + H] +. 1 H MR (δ, ppm, J/Hz): 5.21 (br, 2H, H 2 ), 6.88 (s, 1H). 5-Bromo-thiazol-2-amine 4. [2] Thiazol-2-amine 1 (0.50 g, 5.0 mmol) was dissolved in a 4% aq. HBr (10 ml) placed in a 25-mL round-bottom flask. The brominated was carried out by Br 2 (0.88 g, 5.5 mmol) bubbling through the solution in a stream of air at RT. The reaction mixture was then refluxed for 1 h and cooled down. The formed precipitate was filtered off, dissolved in CHCl 3 (10 ml), H 2 O (5 ml) was added, and the mixture was adjusted to ph 7 at stirring with aq. H 3. The organic fraction was separated, dried over a 2 SO 4, and concentrated on a rotary S3

4 evaporator to give light brow solid. The crude product was purified by column chromatography (ethyl acetate/dichloromethane 1:2) to give a white solid. Yield: 42% (350 mg). M.p. = 103 C. HRESI + -MS: calcd for C 3 H 4 Br 2 S , found m/z [M + H] +. 1 H MR (δ, ppm, J/Hz): 5.05 (br, 2H, H 2 ), 6.97 (s, 1H). 5-Iodo-thiazol-2-amine 5. [4] A solution of thiazol-2-amine 1 (0.50 g, 5.0 mmol) in glacial acetic acid (10 ml) was added to solid I 2 (1.30 g, 5.1 mmol) placed in a 25-mL round-bottom flask and the reaction mixture was stirred in air at RT for 24 h. The solution was diluted with H 2 O (100 ml), adjusted to ph 7 with solid ahco 3, filtered from some insoluble material and extracted with CH 2 Cl 2 (three 15-mL portions). Combined organic fractions were dried over a 2 SO 4, and concentrated on a rotary evaporator to give a light brow solid. The crude product was purified by column chromatography (ethyl acetate/dichloromethane 1:2) to give a white solid. Yield: 45% (510 mg). M.p. = C. HRESI + -MS: calcd for C 3 H 4 I 2 S , found m/z [M + H] +. 1 H MR (δ, ppm, J/Hz): 5.11 (br, 2H, H 2 ), 7.10 (s, 1H). Synthesis of KR (i). A solution any one of 1 9 (0.068 mmol) in CH 2 Cl 2 (3 ml) was added to solid PC (20 mg, mmol) placed in a 10-mL round-bottomed flask. The reaction mixtures were stirred in air at RT for 24 h (48 h in the case of 6) giving KR/TR mixtures enriched with KR. In all cases, the color of the reaction mixtures gradually turned from pale yellow to intense lemon yellow and solid PC was dissolved. The formed solutions were filtered off from some insoluble material and evaporated at C to dryness and then the solid residues were washed with Et 2 O (three 1-mL portions) and dried in air at RT. The yields, isomeric ratios, and elemental analyses data for the obtained mixtures are given in Table S1 (conditions (i)). Pure KRs were obtained by dissolution of these isomeric mixtures enriched with KR in acetone (1.5 ml)/ch 2 Cl 2 (2 ml) mixture and then these solutions were left to evaporate at C to 1 KR = kinetically controlled regioisomer S4

5 ca. 1 ml. In the case of KR9, one additional re-crystallization from acetone/ch 2 Cl 2 mixture was performed. The formed crystals of pure isomers were filtered off, washed with Et 2 O (three 1-mL portions) and dried in air at RT. Pure complexes were obtained as yellow solids and characterized by HRESI + -MS, IR, 1D ( 1 H, 13 C{ 1 H) and 2D ( 1 H, 1 H-COSY, 1 H, 1 H-OESY, 1 H, 13 C-HSQC, 1 H, 13 C-HMBC) MR spectroscopies. Our attempts to isolate pure KR6 failed and this complex was characterized only by 1 H MR as a component of the isomeric mixture. Synthesis of TR (ii). A solution any one of 1 9 (0.068 mmol) in CHCl 3 (5 ml) was added to solid PC (20 mg, mmol) placed in a 10-mL round-bottomed flask. The reaction mixtures were stirred upon reflux for 12 h giving KR/TR mixtures enriched with TR. In all cases, the color of the reaction mixtures gradually turned from pale yellow to intense lemon yellow and solid PC was dissolved. The formed solutions were filtered from some insoluble material and evaporated at C to dryness and then the solid residues were washed with Et 2 O (three 1- ml portions) and dried in air at RT. The yields, isomeric ratios, and elemental analyses data for the obtained mixtures are given in Table S1 (conditions (ii)). Pure TRs were obtained by dissolution of these isomeric mixtures enriched with TR (except TR5, which was obtained from the equilibrium mixture) in acetone (1.5 ml)/ch 2 Cl 2 (2 ml) mixture and then these solutions were left to evaporate at C to ca. 1 ml. In cases of TR8 and TR9, one additional re-crystallization from acetone/ch 2 Cl 2 mixture was performed. The formed crystals of pure isomers were filtered off, washed with Et 2 O (three 1-mL portions) and dried in air at C. Pure complexes were obtained as yellow solids and characterized by HRESI + -MS, IR, 1D ( 1 H, 13 C{ 1 H) and 2D ( 1 H, 1 H-COSY, 1 H, 1 H-OESY, 1 H, 13 C-HSQC, 1 H, 13 C- HMBC) MR spectroscopies. Our attempts to isolate pure TR7 failed and this complex was characterized only by 1 H MR as a component of the certain isomeric mixture. 2 TR = thermodynamically controlled regioisomer S5

6 Table S1. Yields, isomeric ratios, and elemental analyses data for the obtained mixtures Mixture Conditions Yield, % (mg) KR:TR Ratio (%:%) Anal. Calcld. Elemental analyses Found KR1/TR1 KR2/TR2 KR3/TR3 KR4/TR4 KR5/TR5 KR6/TR6 KR7/TR7 KR8/TR8 KR9/TR9 (i) (ii) 92% (19 mg) 87% (18 mg) 85:15 18:82 For C 39 H 38 6 Cl 2 SPd 2 : C, 51.67; H, 4.22;, 9.27 (i) 97% (20 mg) 82:18 For C 40 H 40 6 Cl 2 SPd 2 : (ii) 97% (20 mg) 16:84 C, 52.19; H, 4.38;, 9.13 (i) 90% (19 mg) 71:29 For C 39 H 37 6 Cl 3 SPd 2 CHCl 3 : (ii) 71% (15 mg) 19:81 C, 45.31; H, 3.61;, 7.93 (i) 86% (19 mg) 88:12 For C 39 H 37 6 Cl 2 BrSPd 2 : (ii) 95% (21 mg) 13:87 C, 47.53; H, 3.78;, 8.53 (i) 99% (23 mg) 73:27 For C 39 H 37 6 Cl 2 ISPd 2 : (ii) 30% (MR yield) 28:72 C, 45.37; H, 3.61;, 8.14 (i) 75% (20 mg) 85:15 For C 45 H 42 6 Cl 2 SPd 2 : (ii) 76% (17 mg) 28:72 C, 55.00; H, 4.31;, 8.55 (i) 92% (19 mg) 66:34 For C 38 H 37 Cl 2 7 SPd 2 0.1CHCl 3 : (ii) 82% (17 mg) 57:43 C, 49.77; H, 4.07;, (i) 91% (19 mg) 74:26 For C 39 H 39 Cl 2 7 SPd CH 2 Cl 2 : (ii) 96% (20 mg) 48:52 C, 49.21; H, 4.18;, (i) 94% (21 mg) 55:45 For C 44 H 41 Cl 2 7 SPd CHCl 3 : (ii) 90% (20 mg) 48:52 C, 53.46; H, 4.18;, 9.91 C, 51.51; H, 4.18;, 9.12 C, 52.38; H, 4.23;, 9.03 C, 45.54; H, 3.84;, 7.57 C, 47.40; H, 3.79;, 8.60 C, 45.14; H, 3.30;, 8.14 C, 54.81; H, 4.29;, 8.54 C, 49.85; H, 4.22;, C, 49.60; H, 4.26;, 9.97 C, 53.29; H, 4.27;, Conditions: (i) CH 2 Cl 2, RT; (ii) CHCl 3, reflux S6

7 Regioisomer assignment by 2D MR spectroscopy. From 1 H, 13 C-HMBC and 1 H, 1 H-OESY MR experiments, the regioisomers KR and TR can be clearly distinguished in the solution. In the HMBC spectra of KRs, we found three long-range correlations between the C carbons and the methyl protons of the xylyl groups (Figure S1). The C 1 atom may correlate only with the methyl protons from the xylyl group B. Another C carbon (which included in two palladacycles, C 2 ) may have correlation with the methyl protons from both Xyl groups B and C. We assume that for KRs, the C 1 atom resonates near 195 ppm, whereas the C 2 carbon resonates at ca. 165 ppm. Figure S1. The fragment of the HMBC spectra of KR1 In the case of TRs, two correlations (Figure S2), viz. between the C 1 and the methyl protons in the xylyl group B and between the C 2 atom and the methyl protons in the xylyl group C, were found. S7

8 Figure S2. The fragment of the HMBC spectra of TR1 The assignment of signals from the xylyls B and C was based on the HMBC spectra. The signals of two remaining xylyl groups A and D in the 1 H and 13 C MR spectra for all complexes were preformed based on the OESY spectra. In all cases, there is the through-space interaction between methyl protons in the xylyl group A and B. The same interaction was observed between the methyl protons in the xylyl groups C and D (Figure S3). Furthermore, the cross-peaks between methyl protons in the xylyl groups B and C in the OESY spectra of KRs were observed, but not in the spectra of TRs (Figure S4). In addition to assignments of resonances from the xylyl groups and the C carbons by the HMBC and OESY, we distinguished complexes KRs and TRs in a solution. The assignments of the other 13 C and 1 H signals were performed by 1 H, 1 H-COSY, 1 H, 13 C-HSQC, 1 H, 13 C-HMBC MR methods. S8

9 Figure S3. The fragment of the OESY spectra of TR1. Figure S4. The fragment of the OESY spectra of KR1. S9

10 Characterization data and MR spectra C 5 C 4 S C 2 Pd C 1 Cl Me Xyl= Xyl-D Cl C Xyl-C Pd C 2 C 2 Xyl-B Xyl-A 1 Me KR1. Yield: 63% (13 mg). HRESI + + -MS: calcd for C 39 H 38 6 ClSPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2924 (w), 2852 (w), ν(c ) 2203 (s), ν(=c) 1635 (s), 1474 (s), 1422 (s), δ(c H) 785 (m). 1 H MR (δ, ppm, J/Hz): 2.04 (s, 6H, CH 3, Xyl-C), 2.22 (s, 6H, CH 3, Xyl-D), 2.25 (s, 6H, CH 3, Xyl-A), 2.42 (s, 6H, CH 3, Xyl-B), 6.12 (t, 1H, H 4, Xyl-C, J = 7.5), 6.42 (t, 1H, H 4, Xyl-B, J = 7.6), 6.63 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.85 (d, 1H, H 5, thiazole, J = 4.0), 6.86 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.94 (d, 2H, H 3,5, Xyl-D, J = 7.6), 7.03 (d, 2H, H 3,5, Xyl-A, J = 7.7), 7.12 (t, 1H, H 4, Xyl-D, J = 7.6), 7.19 (t, 1H, H 4, Xyl-A, J = 7.7), 7.86 (d, 1H, H 4, thiazole, J = 4.0). 13 C{ 1 H} MR (δ, ppm): (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-B), (2C, CH 3, Xyl-C), (C 5, thiazole), (C 4, Xyl-C), (C 1, Xyl-A), (2C, C 2,6, Xyl-C), (C 1, Xyl-D), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl-C), (2C, C 3,5, Xyl-A), (2C, C 3,5, Xyl-B), (C 4, Xyl-B), (C 4, Xyl-D), (C 4, Xyl- A), (4C, C 2,6, Xyl-A and -D), (C 4, thiazole), (2C, C 2,6, Xyl-B), (C 1, Xyl-B), (C 1, Xyl-C), (C 2, carbene), (C 2, thiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S10

11 Figure S5. The 1 H MR spectrum of KR1 in CDCl 3 Figure S6. The 13 C{ 1 H} MR spectrum of KR1 in CDCl 3 S11

12 Figure S7. The HMBC MR spectrum of KR1 in CDCl 3 Figure S8. Fragment of the HMBC MR spectrum of KR1 in CDCl 3 S12

13 Xyl-C Xyl-D S C 2 C C 5 C 2 Pd C 4 C 1 Cl Pd Xyl-B Cl C Xyl-A TR1. Yield: 49% (10 mg). HRESI + -MS: calcd for C 39 H 38 6 ClSPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2918 (w), 2851 (w), ν(c ) 2205 (s), ν(=c) 1629 (s), 1557 (s), 1475 (s), δ(c H) 772 (m). 1 H MR (δ, ppm, J/Hz): 2.21 (s, 6H, CH 3, Xyl-D), 2.27 (s, 6H, CH 3, Me Xyl= 2 1 Me Xyl-C), 2.28 (s, 6H, CH 3, Xyl-A), 2.42 (s, 6H, CH 3, Xyl-B), 6.23 (t, 1H, H 4, Xyl-C, J = 7.5), 6.33 (t, 1H, H 4, Xyl-B, J = 7.6), 6.78 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.83 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.94 (d, 1H, H 5, thiazole, J = 4.0), 6.95 (d, 2H, H 3,5, Xyl-D, J = 7.6), 7.04 (d, 2H, H 3,5, Xyl-A, J = 7.6), 7.11 (t, 1H, H 4, Xyl-D, J = 7.6), 7.19 (t, 1H, H 4, Xyl-A, J = 7.6), 8.07 (d, 1H, H 4, thiazole, J = 4.0). 13 C{ 1 H} MR (δ, ppm): (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-C), (2C, CH 3, Xyl-B), (C 5, thiazole), (C 4, Xyl-C), (C 1, Xyl-A), (C 1, Xyl-D), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl-B), (C 4, Xyl-B), (2C, C 3,5, Xyl-A), (2C, C 3,5, Xyl-C), (2C, C 2,6, Xyl-C), (C 4, Xyl-D), (C 4, Xyl-A), (2C, C 2,6, Xyl-B), (2C, C 2,6, Xyl-A), (C 4, thiazole), (2C, C 2,6, Xyl-D), (C 1, Xyl-B), (C 1, Xyl-C), (C 2, carbene), (C 2, thiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms C 6 and C 7 were not found even at high acquisition. S13

14 Figure S9. The 1 H MR spectrum of TR1 in CDCl 3 Figure S10. The 13 C{ 1 H} MR spectrum of TR1 in CDCl 3 S14

15 Figure S11. The HMBC MR spectrum of TR1 in CDCl 3 (ppm) Figure S12. Fragment of the HMBC MR spectrum of TR1 in CDCl 3 S15

16 Me C 5 C 4 S C 2 Pd C 1 Cl Me Xyl= Xyl-D Cl C Xyl-C Pd C 2 C 2 Xyl-B Xyl-A 1 Me KR2. Yield: 68% (14 mg). HRESI + -MS: calcd for C 40 H 40 6 ClSPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2919 (w), 2852 (w), ν(c ) 2194 (s), ν(=c) 1630 (s), 1473 (s), 1437 (s), δ(c H) 774 (m). 1 H MR (δ, ppm, J/Hz): 2.04 (s, 6H, CH 3, Xyl-C), 2.23 (s, 6H, CH 3, Xyl-D), 2.26 (s, 6H, CH 3, Xyl-A), 2.36 (d, 3H, CH 3, thiazole, J = 1.0), 2.42 (s, 6H, CH 3, Xyl-B), 6.12 (t, 1H, H 4, Xyl-C, J = 7.5), 6.42 (t, 1H, H 4, Xyl-B, J = 7.6), 6.63 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.86 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.95 (d, 2H, H 3,5, Xyl-D, J = 7.6), 7.04 (d, 2H, H 3,5, Xyl-A, J = 7.6), 7.10 (t, 1H, H 4, Xyl-D, J = 7.6), 7.19 (t, 1H, H 4, Xyl-A, J = 7.7), 7.54 (d, 1H, H 4, thiazole, J = 1.2). 13 C{ 1 H} MR (δ, ppm): (CH 3, thiazole), (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-B), (2C, CH 3, Xyl-C), (C 4, Xyl-C), (C 1, Xyl-A), (C 5, thiazole), (2C, C 2,6, Xyl-C), (C 1, Xyl-D), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl-C), (4C, C 3,5, Xyl-A and - B), (C 4, Xyl-D), (C 4, Xyl-B), (C 4, Xyl-A), (C 4, thiazole), (2C, C 2,6, Xyl-A), (2C, C 2,6, Xyl-D), (2C, C 2,6, Xyl-B), (C 1, Xyl-B), (C 1, Xyl-C), (C 2, carbene), (C 2, thiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S16

17 Figure S13. The 1 H MR spectrum of KR2 in CDCl 3 Figure S14. The 13 C{ 1 H} MR spectrum of KR2 in CDCl 3 S17

18 Figure S15. The HMBC MR spectrum of KR2 in CDCl 3 Figure S16. Fragment of the HMBC MR spectrum of KR2 in CDCl 3 S18

19 Me Xyl-C Xyl-D S C 2 C C 5 C 2 Pd C 4 C 1 Cl Pd Xyl-B Cl C Xyl-A TR2. Yield: 72% (15 mg). HRESI + -MS: calcd for C 40 H 40 6 ClSPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2971 (w), 2845 (w), ν(c ) 2200 (s), ν(=c) 1637 (s), 1552 (s), 1489 (s), δ(c H) 774 (m). 1 H MR (δ, ppm, J/Hz): 2.21 (s, 6H, CH 3, Xyl-D), Me Xyl= 2 1 Me (s, 6H, CH 3, Xyl-C), 2.28 (s, 6H, CH 3, Xyl-A),2.37 (d, 3H, CH 3, thiazole, J = 1.0), 2.42 (s, 6H, CH 3, Xyl-B), 6.22 (t, 1H, H 4, Xyl-C, J = 7.5), 6.32 (t, 1H, H 4, Xyl-B, J = 7.6), 6.77 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.82 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.94 (d, 2H, H 3,5, Xyl-D, J = 7.6), 7.03 (d, 2H, H 3,5, Xyl-A, J = 7.6), 7.10 (t, 1H, H 4, Xyl-D, J = 7.6), 7.18 (t, 1H, H 4, Xyl-A, J = 7.6), 7.74 (d, 1H, H 4, thiazole, J = 1.2). 13 C{ 1 H} MR (δ, ppm): (CH 3, thiazole), (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-C), (2C, CH 3, Xyl-B), (C 4, Xyl-C), (C 1, Xyl-A), (C 1, Xyl-D), (2C, C 3,5, Xyl-D), (C 5, thiazole), (2C, C 3,5, Xyl-B), (C 4, Xyl-B), (2C, C 3,5, Xyl-A), (2C, C 3,5, Xyl-C), (2C, C 2,6, Xyl-C), (C 4, Xyl-D), (C 4, Xyl-A), (C 4, thiazole), (2C, C 2,6, Xyl-B), (2C, C 2,6, Xyl-A), (2C, C 2,6, Xyl-D), (C 1, Xyl-B), (C 1, Xyl-C), (C 2, thiazole), (C 2, carbene), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S19

20 Figure S17. The 1 H MR spectrum of TR2 in CDCl 3 Figure S18. The 13 C{ 1 H} MR spectrum of TR2 in CDCl 3 S20

21 Figure S19. The HMBC MR spectrum of TR2 in CDCl 3 Figure S20. Fragment of the HMBC MR spectrum of TR2 in CDCl 3 S21

22 Cl C 5 C 4 S C 2 Pd C 1 Cl Me Xyl= Xyl-D Cl C Xyl-C Pd C 2 C 2 Xyl-B Xyl-A 1 Me KR3. Yield: 47% (10 mg). HRESI + -MS: calcd for C 39 H 37 6 Cl 2 SPd , foundm/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2919 (w), 2857 (w), ν(c ) 2208 (s), 2179 (s), ν(=c) 1637 (s), 1473 (s), 1431 (s), δ(c H) 764 (m). 1 H MR (δ, ppm, J/Hz): 2.03 (s, 6H, CH 3, Xyl-C), 2.23 (s, 6H, CH 3, Xyl-D), 2.26 (s, 6H, CH 3, Xyl-A), 2.41 (s, 6H, CH 3, Xyl-B), 6.13 (t, 1H, H 4, Xyl-C, J = 7.5), 6.45 (t, 1H, H 4, Xyl-B, J = 7.6), 6.64 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.87 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.95 (d, 2H, H 3,5, Xyl-D, J = 7.6), 7.05 (d, 2H, H 3,5, Xyl-A, J = 7.6), 7.11 (t, 1H, H 4, Xyl-D, J = 7.6), 7.20 (t, 1H, H 4, Xyl-A, J = 7.7), 7.75 (s, 1H, H 4, thiazole). 13 C{ 1 H} MR (δ, ppm): (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-A), (2C, CH 3, Xyl- B), (2C, CH 3, Xyl-C), (C 5, thiazole), (C 4, Xyl-C), (C 1, Xyl-A), (2C, C 2,6, Xyl-C), (C 1, Xyl-D), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl- C), (2C, C 3,5, Xyl-A), (2C, C 3,5, Xyl-B), (C 4, Xyl-D), (C 4, Xyl-B), (C 4, Xyl-A), (C 4, thiazole), (4C, C 2,6, Xyl-A and -D), (2C, C 2,6, Xyl-B), (C 1, Xyl-B), (C 1, Xyl-C), (C 2, carbene), (C 2, thiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S22

23 Figure S21. The 1 H MR spectrum of KR3 in CDCl 3 Figure S22. The 13 C{ 1 H} MR spectrum of KR3 in CDCl 3 S23

24 Figure S23. The HMBC MR spectrum of KR3 in CDCl 3 Figure S24. Fragment of the HMBC MR spectrum of KR3 in CDCl 3 S24

25 Cl Xyl-C Xyl-D S C 2 C C 5 C 2 Pd C 4 C 1 Cl Pd Xyl-B Cl C Xyl-A TR3. Yield: 71% (15 mg). HRESI + -MS: calcd for C 39 H 37 6 Cl 2 SPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ):ν(c H) 2919 (w), 2846 (w), ν(c ) 2204 (s), 2191 (s), ν(=c) 1630 (s), 1552 (s), 1487 (s), δ(c H) 774 (m). 1 H MR (δ, ppm, J/Hz): 2.20 (s, 6H, CH 3, Me Xyl= 2 1 Me Xyl-D), 2.26 (s, 6H, CH 3, Xyl-C), 2.27 (s, 6H, CH 3, Xyl-A), 2.41 (s, 6H, CH 3, Xyl-B), 6.24 (t, 1H, H 4, Xyl-C, J = 7.5), 6.33 (t, 1H, H 4, Xyl-B, J = 7.5), 6.78 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.83 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.94 (d, 2H, H 3,5, Xyl-D, J = 7.6), 7.04 (d, 2H, H 3,5, Xyl-A, J = 7.6), 7.11 (t, 1H, H 4, Xyl-D, J = 7.6), 7.19 (t, 1H, H 4, Xyl-A, J = 7.6), 7.94 (s, 1H, H 4, thiazole). 13 C{ 1 H} MR (δ, ppm): (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-C), (2C, CH 3, Xyl-B), (C5, thiazole), (C 4, Xyl-C), (2C, C 1, Xyl-A and -D), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl-B), (2C, C 3,5, Xyl-A), (C 4, Xyl-B), (2C, C 3,5, Xyl-C), (2C, C 2,6, Xyl-C), (C 4, Xyl-D), (C 4, Xyl-A), (C 4, thiazole), (2C, C 2,6, Xyl-B), (2C, C 2,6, Xyl-A), (2C, C 2,6, Xyl-D), (C 1, Xyl-B), (C 1, Xyl-C), (C 2, thiazole), (C 2, carbene), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S25

26 Figure S25. The 1 H MR spectrum of TR3 in CDCl 3 Figure S26. The 13 C{ 1 H} MR spectrum of TR3 in CDCl 3 S26

27 Figure S27. The HMBC MR spectrum of TR3 in CDCl 3 Figure S28. Fragment of the HMBC MR spectrum of TR3 in CDCl 3 S27

28 Br C 5 C 4 S C 2 Pd C 1 Cl Me Xyl= Xyl-D Cl C Xyl-C Pd C 2 C 2 Xyl-B Xyl-A 1 Me KR4. Yield: 68% (15 mg). HRESI + -MS: calcd for C 39 H 37 6 ClBrSPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2924 (s), 2852 (s), ν(c ) 2204 (s), ν(=c) 1635 (s), 1480 (s), 1429 (s), δ(c H) 776 (m). 1 H MR (δ, ppm, J/Hz): 2.04 (s, 6H, CH 3, Xyl-C), 2.23 (s, 6H, CH 3, Xyl-D), 2.26 (s, 6H, CH 3, Xyl-A), 2.41 (s, 6H, CH 3, Xyl-B), 6.14 (t, 1H, H 4, Xyl-C, J = 7.5), 6.44 (t, 1H, H 4, Xyl-B, J = 7.5), 6.64 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.87 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.96 (d, 2H, H 3,5, Xyl-D, J = 7.6), 7.05 (d, 2H, H 3,5, Xyl-A, J = 7.6), 7.11 (t, 1H, H 4, Xyl-D, J = 7.6), 7.20 (t, 1H, H 4, Xyl-A, J = 7.7), 7.83 (s, 1H, H 4, thiazole). 13 C{ 1 H} MR (δ, ppm): (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-B), (2C, CH 3, Xyl-C), (C 5, thiazole), (C 4, Xyl-C), (C 1, Xyl-A), (2C, C 2,6, Xyl-C), (C 1, Xyl-D), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl-C), (2C, C 3,5, Xyl-A), (2C, C 3,5, Xyl-B), (C 4, Xyl-D), (C 4, Xyl-B), (C 4, Xyl-A), (C 4, thiazole), (4C, C 2,6, Xyl-A), (4C, C 2,6, Xyl -D), (2C, C 2,6, Xyl-B), (C 1, Xyl-B), (C 1, Xyl-C), (C 2, carbene), (C 2, thiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S28

29 Figure S29. The 1 H MR spectrum of KR4 in CDCl 3 Figure S30. The 13 C{ 1 H} MR spectrum of KR4 in CDCl 3 S29

30 Figure S31. The HMBC MR spectrum of KR4 in CDCl 3 Figure S32. Fragment of the HMBC MR spectrum of KR4 in CDCl 3 S30

31 Br Xyl-C Xyl-D S C 2 C C 5 C 2 Pd C 4 C 1 Cl Pd Xyl-B Cl C Xyl-A TR4. Yield: 77% (17 mg). HRESI + -MS: calcd for C 39 H 37 6 ClBrSPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2924 (w), 2852 (w), ν(c ) 2204 (s), ν(=c) 1631 (s), 1554 (s), 1483 (s), δ(c H) 774 (m). 1 H MR (δ, ppm, J/Hz): 2.20 (s, 6H, CH 3, Xyl-D), Me Xyl= 2 1 Me (s, 6H, CH 3, Xyl-C), 2.27 (s, 6H, CH 3, Xyl-A), 2.41 (s, 6H, CH 3, Xyl-B), 6.24 (t, 1H, H 4, Xyl-C, J = 7.5), 6.33 (t, 1H, H 4, Xyl-B, J = 7.5), 6.78 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.83 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.94 (d, 2H, H 3,5, Xyl-D, J = 7.6), 7.04 (d, 2H, H 3,5, Xyl-A, J = 7.6), 7.11 (t, 1H, H 4, Xyl-D, J = 7.6), 7.19 (t, 1H, H 4, Xyl-A, J = 7.6), 8.02 (s, 1H, H 4, thiazole). 13 C{ 1 H} MR (δ, ppm): (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-C), (2C, CH 3, Xyl-B), (C 5, thiazole), (C 4, Xyl-C), (2C, C 1, Xyl-A and - D), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl-B), (2C, C 3,5, Xyl-A), (C 4, Xyl-B), (2C, C 3,5, Xyl-C), (2C, C 2,6, Xyl-C), (C 4, Xyl-D), (C 4, Xyl-A), (2C, C 2,6, Xyl-B), (C 4, thiazole), (2C, C 2,6, Xyl-A), (2C, C 2,6, Xyl-D), (C 1, Xyl-B), (C 1, Xyl-C), (C 2, carbene), (C 2, thiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S31

32 Figure S33. The 1 H MR spectrum of TR4 in CDCl 3 Figure S34. The 13 C{ 1 H} MR spectrum of TR4 in CDCl 3 S32

33 Figure S35. The HMBC MR spectrum of TR4 in CDCl 3 Figure S36. Fragment of the HMBC MR spectrum of TR4 in CDCl 3 S33

34 I C 5 C 4 S C 2 Pd C 1 Cl Me Xyl= Xyl-D Cl C Xyl-C Pd C 2 C 2 Xyl-B Xyl-A 1 Me KR5. Yield: 65% (15 mg). HRESI + -MS: calcd for C 39 H 37 6 ClISPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2924 (w), 2852 (w), ν(c ) 2199 (s), ν(=c) 1636 (s), 1473 (s), 1426 (s), δ(c H) 774 (m). 1 H MR (δ, ppm, J/Hz): 2.03 (s, 6H, CH 3, Xyl-C), 2.23 (s, 6H, CH 3, Xyl-D), 2.26 (s, 6H, CH 3, Xyl-A), 2.41 (s, 6H, CH 3, Xyl-B), 6.13 (t, 1H, H 4, Xyl-C, J = 7.5), 6.44 (t, 1H, H 4, Xyl-B, J = 7.6), 6.64 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.87 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.95 (d, 2H, H 3,5, Xyl-D, J = 7.6), 7.04 (d, 2H, H 3,5, Xyl-A, J = 7.6), 7.11 (t, 1H, H 4, Xyl-D, J = 7.6), 7.20 (t, 1H, H 4, Xyl-A, J = 7.6), 7.93 (s, 1H, H 4, thiazole). 13 C{ 1 H} MR (δ, ppm): (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-B), (2C, CH 3, Xyl-C), (C 5, thiazole), (C 4, Xyl-C), (C 1, Xyl-A), (2C, C 2,6, Xyl-C), (C 1, Xyl-D), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl-C), (2C, C 3,5, Xyl-A), (2C, C 3,5, Xyl-B), (C 4, Xyl-D), (C 4, Xyl-B), (C 4, Xyl-A), (4C, C 2,6, Xyl-A and -D), (2C, C 2,6, Xyl-B), (C 4, thiazole), (C 1, Xyl-B), (C 1, Xyl-C), (C 2, carbene), (C 2, thiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S34

35 Figure S37. The 1 H MR spectrum of KR5 in CDCl 3 Figure S38. The 13 C{ 1 H} MR spectrum of KR5 in CDCl 3 S35

36 Figure S39. The HMBC MR spectrum of KR5 in CDCl 3 Figure S40. Fragment of the HMBC MR spectrum of KR5 in CDCl 3 S36

37 I Xyl-C Xyl-D S C 2 C C 5 C 2 Pd C 4 C 1 Cl Pd Xyl-B Cl C Xyl-A TR5. Yield: 47% (11 mg). HRESI + -MS: calcd for C 39 H 37 6 ClISPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2913 (w), 2840 (w), ν(c ) 2199 (s), ν(=c) 1630 (s), 1555 (s), 1474 (s), δ(c H) 773 (m). 1 H MR (δ, ppm, J/Hz): 2.21 (s, 6H, CH 3, Xyl-D), 2.26 (s, 6H, Me Xyl= 2 1 Me CH 3, Xyl-C), 2.27 (s, 6H, CH 3, Xyl-A), 2.41 (s, 6H, CH 3, Xyl-B), 6.24 (t, 1H, H 4, Xyl-C, J = 7.5), 6.33 (t, 1H, H 4, Xyl-B, J = 7.5), 6.78 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.83 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.94 (d, 2H, H 3,5, Xyl-D, J = 7.6), 7.04 (d, 2H, H 3,5, Xyl-A, J = 7.7), 7.11 (t, 1H, H 4, Xyl-D, J = 7.6), 7.19 (t, 1H, H 4, Xyl-A, J = 7.6), 8.11 (s, 1H, H 4, thiazole). 13 C{ 1 H} MR (δ, ppm): (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-C), (2C, CH 3, Xyl-B), (C 5, thiazole), (C 4, Xyl-C), (2C, C 1, Xyl-A and -D), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl-B), (2C, C 3,5, Xyl-A), (C 4, Xyl-B), (2C, C 3,5, Xyl-C), (2C, C 2,6, Xyl-C), (C 4, Xyl-D), (C 4, Xyl-A), (2C, C 2,6, Xyl-B), (2C, C 2,6, Xyl-A), (2C, C 2,6, Xyl-D), (C 4, thiazole), (C 1, Xyl-B), (C 1, Xyl-C), (C 2, carbene), (C 2, thiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S37

38 Figure S41. The 1 H MR spectrum of TR5 in CDCl 3 Figure S42. The 13 C{ 1 H} MR spectrum of TR5 in CDCl 3 S38

39 Figure S43. The HMBC MR spectrum of TR5 in CDCl 3 Figure S44. Fragment of the HMBC MR spectrum of TR5 in CDCl 3 S39

40 C 5 C S C 2 Pd C 1 Cl Me Xyl= Xyl-D Cl C Xyl-C Pd C 2 C 2 Xyl-B Xyl-A 1 Me KR6. The complex was characterized only by 1 H MR as a component of the isomeric mixture with TR6. 1H MR (δ, ppm, J/Hz): 2.08 (s, 6H, CH 3, Xyl-A and -C), 2.22 (s, 6H, CH 3, Xyl-D), 2.26 (s, 6H, CH 3, Xyl-B), 2.48 (s, 6H, CH 3, Xyl- C), 6.19 (t, 1H, H 4, Xyl-C, J = 7.5), 6.56 (t, 1H, H 4, Xyl-B, J = 7.6), 6.67 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.71 (s, 1H, H 5, thiazole), 6.88 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.98 (d, 2H H 3,5, Xyl-D, J = 7.6), 7.01 (d, 2H, H 3,5, Xyl-A, J = 7.3), (m, 2H, H 4, Xyl-A and -D), (m, 3H, H 3,4,5, Ph) (m, 2H, H 2,6, Ph). S40

41 C 5 C S C 2 Pd C 1 Cl Me Xyl= C 2 Xyl-C Xyl-D C C 2 Pd Cl Xyl-B Xyl-A 1 Me TR6. Yield: 40% (9 mg). HRESI + -MS: (calcd for C 45 H 42 Cl 6 SPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2925 (s), 2860 (s), ν(c ) 2209 (s), 2194 (s), ν(=c) 1634 (s), 1550 (s), 1480 (s), δ(c H) 778 (m). 1 H MR (δ, ppm, J/Hz): 2.22 (s, 12H, CH 3, Xyl-A, CH 3, Xyl-D), 2.31 (s, 6H, CH 3, Xyl-C), 2.46 (s, 6H, CH 3, Xyl-B), 6.25 (t, 1H, H 4, Xyl-C, J = 7.5), 6.39 (t, 1H, H 4, Xyl-B, J = 7.5), 6.76 (s, 1H, H 5, thiazole), 6.80 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.82 (d, 2H, H 3,5, Xyl-B, J = 7.5), 6.95 (d, 2H, H 3,5, Xyl-D, J = 8.0), 6.97 (d, 2H, H 3,5, Xyl-A, J = 8.0), 7.11 (t, 1H, H 4, Xyl-D, J = 7.5), 7.13 (t, 1H, H 4, Xyl-A, J = 8.0), 7.38 (m, 3H, H 3,4,5, Ph) 7.51 (m, 2H, H 2,6, Ph). 13 C{ 1 H} MR (δ, ppm): (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-B), (2C, CH 3, Xyl-C), (C 5, thiazole), (C 4, Xyl-C), (2C, C 1, Xyl-A and -D), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl-B), (2C, C 3,5, Xyl-A), (3C, C 4, Xyl-B and C 2,6, Ph), (2C, C 3,5, Xyl-C), (2C, C 2,6, Xyl-C), (C 4, Ph), (C 4, Xyl-D), (C 4, Xyl-A), (2C, C 3,5, Ph), (2C, C 2,6, Xyl-B), (C 1, Ph), (2C, C 2,6, Xyl-A), (2C, C 2,6, Xyl-D), (C 1, Xyl-B), (C 1, Xyl-C), (C 4, thiazole), (C 2, carbene), (C 2, thiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S41

42 Figure S45. The 1 H MR spectrum of TR6 in CDCl 3 Figure S46. The 13 C{ 1 H} MR spectrum of TR6 in CDCl 3 S42

43 Figure S47. The HMBC MR spectrum of TR6 in CDCl 3 Figure S48. Fragment of the HMBC MR spectrum of TR6 in CDCl 3 S43

44 C 5 S C 2 Pd C 1 Cl Me Xyl= Xyl-D Cl C Xyl-C Pd C 2 C 2 Xyl-B Xyl-A 1 Me KR7. Yield: 43% (9 mg). HRESI + + -MS: calcd for C 38 H 37 Cl 7 SPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2923 (s), 2851 (s), ν(c ) 2203 (s), ν(=c) 1636 (s), 1475 (s), 1420 (s), δ(c H) 783 (m). 1 H MR (δ, ppm, J/Hz): 2.05 (s, 6H, CH 3, Xyl-C), 2.23 (s, 6H, CH 3, Xyl-D), 2.26 (s, 6H, CH 3, Xyl-A), 2.42 (s, 6H, CH 3, Xyl-B), 6.15 (t, 1H, H 4, Xyl-C, J = 7.51), 6.47 (t, 1H, H 4, Xyl-B, J = 7.5), 6.65 (d, 2H, H 3,5, Xyl-C, J = 7.6), 6.90 (d, 2H, H 3,5, Xyl-B, J = 7.5), 6.96 (d, 2H, H 3,5, Xyl-D, J = 7.6), 7.04 (d, 2H, H 3,5, Xyl-A, J = 7.6), 7.12 (t, 1H, H 4, Xyl-D, J = 7.6), 7.20 (t, 1H, H 4, Xyl-A, J = 7.6), 8.62 (s, 1H, H 5, thiadiazole). 13 C{ 1 H} MR (δ, ppm): (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-B), (2C, CH 3, Xyl-C), (C 4, Xyl-C), (C 1, Xyl-A), (2C, C 2,6, Xyl-C), (C 1, Xyl-D), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl-C), (2C, C 3,5, Xyl-A), (2C, C 3,5, Xyl-B), (C 4, Xyl-D), (C 4, Xyl-A), (C 4, Xyl-B), (2C, C 2,6, Xyl-A and -D), (2C, C 2,6, Xyl- B), (C 1, Xyl-B), (C 5, thiadiazole), (C 1, Xyl-C), (C 2, carbene), (C 2, thiadiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S44

45 Figure S49. The 1 H MR spectrum of KR7 in CDCl 3 Figure S50. The 13 C{ 1 H} MR spectrum of KR7 in CDCl 3 S45

46 Figure S51. The HMBC MR spectrum of KR7 in CDCl 3 Figure S52. Fragment of the HMBC MR spectrum of KR7 in CDCl 3 S46

47 Xyl-C Xyl-D S C 2 C C 5 C 2 Pd C 1 Cl Pd Xyl-B Cl C Me Xyl= 2 Xyl-A 1 Me TR7. The complex was characterized only by 1 H MR as a component of the isomeric mixture with KR7. 1 H MR (δ, ppm, J/Hz): 2.23 (s, 6H, CH3, Xyl-D), 2.27 (s, 6H, CH3, Xyl-C), 2.30 (s, 6H, CH3, Xyl-A), 2.62 (s, 6H, CH 3, Xyl-B), 6.28 (t, 1H, H 4, Xyl-C, J = 7.5), 6.38 (t, 1H, H 4, Xyl-B, J = 7.5), 6.81 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.87 (d, 2H, H 3,5, Xyl-B, J = 7.5), 6.97 (d, 2H, H 3,5, Xyl-D, J = 7.5), 7.05 (d, 2H, H 3,5, Xyl-A, J = 7.5), (m, 2H, H 4, Xyl-A and -D), 8.79 (s, 1H, H 5, thiаdiazole). S47

48 Me C 5 S C 2 Pd C 1 Cl Me Xyl= Xyl-D Cl C Xyl-C Pd C 2 C 2 Xyl-B Xyl-A 1 Me KR8. Yield: 48% (10 mg). HRESI + -MS: calcd for C 39 H 39 Cl 7 SPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2916 (w), 2849 (s), ν(c ) 2206 (s), 2193 (s), ν(=c) 1634 (s), 1475 (s), 1421 (s), δ(c H) 775 (m). 1 H MR (δ, ppm, J/Hz): 2.04 (s, 6H, CH 3, Xyl-D), 2.23 (s, 6H, CH 3, Xyl-C), 2.25(s, 6H, CH 3, Xyl-A), 2.41 (s, 6H, CH 3, Xyl-B), 2.69 (s, 3H, CH 3, thiadiazole), 6.14 (t, 1H, H 4, Xyl-C, J = 7.5), 6.46 (t, 1H, H 4, Xyl-B, J = 7.6), 6.64 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.88 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.96 (d, 2H, H 3,5, Xyl-D, J = 7.6), 7.03 (d, 2H, H 3,5, Xyl-A, J = 7.7), 7.11 (t, 1H, H 4, Xyl-D, J = 7.6), 7.19 (t, 1H, H 4, Xyl-A, J = 7.7). 13 C{ 1 H} MR (δ, ppm): (CH 3, thiadiazole), (2C, CH 3, Xyl- D), (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-B), (2C, CH 3, Xyl-C), (C 4, Xyl- C), (C 1, Xyl-A), (2C, C 2,6, Xyl-C), (C 1, Xyl-D), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl-B), (2C, C 3,5, Xyl-A), (2C, C 3,5, Xyl-C), (C 4, Xyl- D), (C 4, Xyl-A), (C 4, Xyl-B), (4C, C 2,6, Xyl-A and -D), (2C, C 2,6, Xyl-B), (C 1, Xyl-B), (C 1, Xyl-C), (C 5, thiadiazole), (C 2, carbene), (C 2, thiadiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S48

49 Figure S53. The 1 H MR spectrum of KR8 in CDCl 3 Figure S54. The 13 C{ 1 H} MR spectrum of KR8 in CDCl 3 S49

50 Figure S55. The HMBC MR spectrum of KR8 in CDCl 3 Figure S56. Fragment of the HMBC MR spectrum of KR8 in CDCl 3 S50

51 Me C 5 S C 2 Pd C 1 Cl C Xyl-C Xyl-D C C 2 Pd Cl Xyl-B Xyl-A TR8. Yield: 29% (6 mg). HRESI + -MS: calcd for C 39 H 39 Cl 7 SPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2928 (s), 2849 (s), ν(c ) 2208 (s), ν(=c) 1630 (s), 1550 (s), 1463 (s), δ(c H) 764 (m). 1 H MR (δ, ppm, J/Hz): (s, 6H, CH 3, Xyl-D), Me Xyl= 2 1 Me (s, 6H, CH 3, Xyl-C), 2.27 (s, 6H, CH 3, Xyl-A), 2.41 (s, 6H, CH 3, Xyl-B), 2.72 (CH 3, thiadiazole), 6.24 (t, 1H, H 4, Xyl- C, J = 7.5), 6.35 (t, 1H, H 4, Xyl-B, J = 7.6), 6.78 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.84 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.94 (d, 2H, H 3,5, Xyl-D, J = 7.6), 7.02 (d, 2H, H 3,5, Xyl-A, J = 7.7), 7.11 (t, 1H, H 4, Xyl-D, J = 7.6), 7.17 (t, 1H, H 4, Xyl-A, J = 7.7). 13 C{ 1 H} MR (δ, ppm): (CH 3, thiadiazole), (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-B), (2C, CH 3, Xyl-C), (C 4, Xyl-C), (2, C 1, Xyl-A and -D), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl-B), (2C, C 3,5, Xyl-A), (C 4, Xyl-B), (2C, C 3,5, Xyl-C), (2C, C 2,6, Xyl-C), (C 4, Xyl-D), (C 4, Xyl-A), (2C, C 2,6, Xyl-B), (2C, C 2,6, Xyl-A), (2C, C 2,6, Xyl- D), (2С, C 1, Xyl-C and -B), (C 2, carbene), (C 5, thiadiazole), (C 2, thiadiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S51

52 Figure S57. The 1 H MR spectrum of TR8 in CDCl 3 Figure S58. The 13 C{ 1 H} MR spectrum of TR8 in CDCl 3 S52

53 Figure S59. The HMBC MR spectrum of TR8 in CDCl 3 Figure S60. Fragment of the HMBC MR spectrum of TR8 in CDCl 3 S53

54 C 5 S C 2 Pd C 1 Cl Me Xyl= Xyl-D Cl C Xyl-C Pd C 2 C 2 Xyl-B Xyl-A 1 Me KR9. Yield: 36% (8 mg). HRESI + -MS: calcd for C 44 H 41 Cl 7 SPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2916 (w), 2849 (w), ν(c ) 2194 (s), ν(=c) 1633 (s), 1474 (s), 1415 (s), δ(c H) 761 (m). 1 H MR (δ, ppm, J/Hz): 2.05 (s, 6H, CH 3, Xyl-D), 2.24 (s, 6H, CH 3, Xyl-C), 2.27(s, 6H, CH 3, Xyl-A), 2.43 (s, 6H, CH 3, Xyl-B), 6.14 (t, 1H, H 4, Xyl-C, J = 7.5), 6.47 (t, 1H, H 4, Xyl-B, J = 7.6), 6.65 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.90 (d, 2H, H 3,5, Xyl-B, J = 7.6), 6.97 (d, 2H, H 3,5, Xyl- D, J = 7.7), 7.05 (d, 2H, H 3,5, Xyl-A, J = 7.7), 7.12 (t, 1H, H 4, Xyl-D, J = 7.7), 7.20 (t, 1H, H 4, Xyl-A, J = 7.7), (m, 3H, H 2,4,6, Ph), 7.97 (dd, 2H, H 3,5, Ph, J = 7.4/2.2). 13 C{ 1 H} MR (δ, ppm): (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-B), (2C, CH 3, Xyl-C), (C 4, Xyl-C), (C 1, Xyl-A), (2C, C 2,6, Xyl-C), (C 1, Xyl-D), (2C, C 2,6, Ph), (2C, C 3,5, Xyl-D), (2C, C 3,5, Xyl-B), (2C, C 3,5, Xyl-A), (2C, C 3,5, Xyl-C), (2C, C 3,5, Ph), (C 4, Xyl-D), (C 4, Xyl-A), (C 4, Xyl-B), (C 4,Ph), (4C, C 2,6, Xyl-A and -D), (2C, C 2,6, Xyl-B), (C 1, Xyl-B), (C 1, Xyl-C), (C 5, thiadiazole), (C 2, carbene), (C 2, thiadiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S54

55 Figure S61. The 1 H MR spectrum of KR9 in CDCl 3 Figure S62. The 13 C{ 1 H} MR spectrum of KR9 in CDCl 3 S55

56 Figure S63. The HMBC MR spectrum of KR9 in CDCl 3 Figure S64. Fragment of the HMBC MR spectrum of KR9 in CDCl 3 S56

57 Xyl-C Xyl-D S C 2 C C 5 C 2 Pd C 1 Cl Pd Xyl-B Cl C Xyl-A TR9. Yield: 32% (7 mg). HRESI + -MS: calcd for C 44 H 41 Cl 7 SPd , found m/z [M Cl] +. IR (KBr, selected bands, cm 1 ): ν(c H) 2924 (s), 2851 (s), ν(c ) 2211 (s), 2195 (s), ν(=c) 1628 (s), 1551 (s), 1460 (s), δ(c H) 767 (m). 1 H MR (δ, ppm, Me Xyl= 2 1 Me J/Hz): 2.24 (s, 6H, CH 3, Xyl-D), 2.30 (s, 6H, CH 3, Xyl-C), 2.31 (s, 6H, CH 3, Xyl-A), 2.46 (s, 6H, CH 3, Xyl-B), 6.29 (t, 1H, H 4, Xyl-C, J = 7.5), 6.38 (t, 1H, H 4, Xyl-B, J = 7.5), 6.83 (d, 2H, H 3,5, Xyl-C, J = 7.5), 6.88 (d, 2H, H 3,5, Xyl-B, J = 7.5), 6.98 (d, 2H,H 3,5, Xyl-D, J = 7.6), 7.06 (d, 2H, H 3,5, Xyl-A, J = 7.6), 7.14 (t, 1H, H 4, Xyl-D, J = 7.6), 7.21 (t, 1H, H 4, Xyl-A, J = 7.6), (m, 3H, H 2,4,6, Ph), 7.97 (dd, 2H, H 3,5, Ph, J = 7.9/1.5). 13 C{ 1 H} MR (δ, ppm): (2C, CH 3, Xyl-A), (2C, CH 3, Xyl-D), (2C, CH 3, Xyl-C), (2C, CH 3, Xyl-B), (C 4, Xyl-C), (2C, C 1, Xyl-D and -A), (4C, C 3,5, Xyl-D and C 2,6, Ph), (2C, C 3,5, Xyl-B), (2C, C 3,5, Xyl-A), (2C, C 3,5, Xyl-C), (C 4, Xyl-B), (2C, C 2,6, Xyl-C), (2C, C 3,5, Ph), (C 4, Xyl-D), (C 4, Xyl-A), (C 1, Ph), (C 4, Ph), (2C, C 2,6, Xyl-B), (2C, C 2,6, Xyl-A), (2C, C 2,6, Xyl-D), (2C, C 1, Xyl-B and -C), (C 2, carbene), (C 2, thiadiazole), (C 5, thiadiazole), (C 1, carbene). The signals of the isocyanide quaternary atoms by Xyl-A and Xyl-D were not found even at high acquisition. S57

58 Figure S65. The 1 H MR spectrum of TR9 in CDCl 3 Figure S66. The HMBC MR spectrum of TR9 in CDCl 3 S58

59 Figure S67. HMBC MR spectrum of TR9 in CDCl 3 Figure S68. Fragment of the HMBC MR spectrum of TR9 in CDCl 3 S59

60 X-ray Structure Determinations Single-crystals of KR1, KR7, TR8, and KR9 were grown from acetone/ch 2 Cl 2 mixtures and that of TR1 and TR7 from a Et 2 O/CHCl 3 mixture. The X-ray experiments were conducted on a Superova, Dual, Cu at zero, Atlas diffractometer of KR1, TR1 and on a Xcalibur, Eos diffractometer of KR7, TR7, TR8, and KR9. The crystals were kept at 100(2) K during data collection. Using Olex2, [5] the structure was solved with the Superflip [6] structure solution program using Charge Flipping (KR1, TR8) and with the ShelXS [6] using Direct Methods (TR1, KR7, TR7, KR9) and all structures were refined with the ShelXL [6] refinement package using Least Squares minimization. The carbon-bound H atoms were placed in calculated positions and were included in the refinement in the riding model approximation, with U iso (H) set to 1.5U eq (C) and C H 0.96 Å for the CH 3 groups, with U iso (H) set to 1.2U eq (C) and C H 0.93 Å for the CH groups. Empirical absorption correction was applied in CrysAlisPro [7] program complex using spherical harmonics implemented in SCALE3 ABSPACK scaling algorithm. The crystal data, data collection parameters, and structure refinement data of KR1, KR7, KR9, TR1, TR7 and TR8 are given in Table S3. S60

61 Table S2. Crystal data and structure refinement Identification code KR1 TR1 KR7 TR7 TR8 KR9 Empirical formula C 39 H 38 6 SCl 2 P d 2 C 43 H 48 Cl 2 6 S Pd 2 O C 38 H 37 7 SCl 2 Pd 2 C 39 H 38 Cl 5 7 Pd2S C 40 H 41 Cl 4 7 Pd 2 S C 90 H S 2 Cl 4 Pd 4O Formula weight Temperature/K 100(2) 100(2) 100(2) 100(2) 100(2) 100(2) Crystal system triclinic monoclinic triclinic monoclinic orthorhombic monoclinic Space group P-1 P2 1 /c P-1 P21/c P P2 1 /c a/å (2) (12) (15) (3) (14) (6) b/å (3) (3) (2) (9) (3) (10) c/å (9) (5) (6) (11) (4) (7) α/ (3) (18) β/ (2) (14) (16) (4) (4) γ/ (3) (19) Volume/Å (11) (12) (7) (3) (12) (3) Z ρ calc mg/mm m/mm F(000) Crystal size/mm Θ range for data 5.82 to to 5.28 to to to to 55 collection Index ranges -9 h 6, -10 k 10, -37 l h 7, - 24 k 24, - 33 l 34-9 h 9, -10 k 10, -39 l h 10, -23 k 24, -36 l h 10, -25 k 25, -35 l h 14, -15 k 26, -19 l 19 Reflections collected Independent reflections 7256[R(int) = ] 8963[R(int) = ] 8428[R(int) = ] 9549 [Rint = , Rsigma = ] 9844 [R int = , R sigma = ] 9729[R(int) = ] Data/restraints/para 7256/0/ /3/ /0/ /0/ /0/ /0/528 meters Goodness-of-fit on F 2 Final R indexes [I>=2σ (I)] R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = R1 = , wr2 = R 1 = , wr 2 = R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = R1 = , wr2 = R 1 = , wr 2 = R 1 = , wr 2 = Largest diff. 2.37/ / / / / /-1.83 peak/hole / e Å -3 Flack parameter (10) umber of CCDC a R1 = Σ F o F c /Σ F o. b wr2 = [Σ[w(F o 2 F c 2 ) 2 ]/ Σ[w(F o 2 ) 2 ]] 1/2. S61

62 Computational Details The full geometry optimization and single point calculations based on the experimental X-ray geometries (quasi-solid-state approach) have been carried out at DFT level of theory using the M06 functional [8] (this functional was specifically developed to describe weak dispersion forces and non-covalent interactions) with the help of Gaussian-09 [9] program package. The calculations were performed using the quasi-relativistic Stuttgart pseudopotentials that described 28 core electrons and the appropriate contracted basis sets [10] for the palladium atoms and the 6-31G* basis sets for other atoms. o symmetry restrictions have been applied during the geometry optimization. The solvent effects were taken into account using the SMD continuum solvation model by Truhlar et al. [11] with CHCl 3 as solvent. The Hessian matrix was calculated analytically for the optimized structures in order to prove the location of correct minima (no imaginary frequencies), and to estimate the thermodynamic parameters, the latter being calculated at 25 C. The topological analysis of the electron density distribution with the help of the atoms in molecules (AIM) method developed by Bader [12] has been performed by using the Multiwfn program (version 3.3.4). [13] The Wiberg bond indices were computed by using the natural bond orbital (BO) partitioning scheme. [14] The Cartesian atomic coordinates of the calculated equilibrium structures in CHCl 3 solution are presented in Table S5. S62

63 Table S3. Values of the density of all electrons ρ(r), Laplacian of electron density 2 ρ(r), energy density H b, potential energy density V(r), and Lagrangian kinetic energy G(r) (Hartree) at the bond critical points (3, 1), corresponding to the chalcogen bonding S Cl and S in KR/TR1 and KR/TR7 for both solid state (normal text) and CHCl 3 solution (bold text), appropriate bonds lengths d (Å) as well as energies for these non-covalent interactions E int (kcal/mol), defined by two approaches Contact Phase ρ(r) 2 ρ(r) H b V(r) G(r) E int a E int b d KR1 S Cl Solid state CHCl 3 solution TR1 S Solid state CHCl 3 solution KR7 S Cl Solid state CHCl S63

64 solution TR7 S Solid state CHCl3 solution a E int = V(r)/2 [15] b E int = 0.429G(r) [16] Table S4. Calculated total energies, enthalpies, Gibbs free energies (in Hartree) and entropies (in cal/mol K) (E s, H s, G s, S s ) for the optimized structures of KR1, TR1, KR7 and TR7 in CHCl 3 solution Compound E s H s S s G s KR TR KR TR Table S5. Сartesian atomic coordinates of the calculated equilibrium structures of KR1, TR1, KR7 and TR7 in CHCl 3 solution. uclear charges of elements are shown in the second column Compound Charge X Y Z TR S64

65 S65