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1 S1 Supporting information for the article Efficient General Procedure To Access a Diversity of Gold(0) Particles and Gold(I) Phosphine Complexes from a Simple HAuCl 4 Source. Localization of Homogeneous/Heterogeneous System s Interface and Field-Emission Scanning Electron Microscopy Study Sergey S. Zalesskiy, Alexander E. Sedykh, Alexey S. Kashin, and Valentine P. Ananikov * Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow, , Russia. val@ioc.ac.ru; Fax: +007 (499) CONTENTS S1. Optimization of reaction conditions for the preparation of (PPh 3 )AuCl....2 S2. Summary of the 31 P{ 1 H} NMR data for the prepared complexes....5 S3. Characterization of the synthesized (R 3 P)AuCl complexes....5 S4. 31 P{ 1 H} NMR spectra of the prepared complexes...8 S5. 13 C{ 1 H} NMR spectra of the prepared complexes S6. ESI-MS data for the prepared complexes...20

2 S2 S1. Optimization of reaction conditions for the preparation of (PPh 3 )AuCl. On the first step of optimization we tested several sulfides towards activity in Au(III) reduction (Scheme S1). It would be preferable to utilize solid non-volatile sulfides (such as (PhCH 2 ) 2 S) in the reaction, however the latter showed almost no activity in the reduction process. Diethyl sulfide demonstrated moderate activity (82% yield of complex in the protocol developed), yet the best reagent among the tested compounds was Pr 2 S, which gave the highest yield. In addition, significantly lower volatility of Pr 2 S compared to Et 2 S (vapor pressures of and 94.4 mmhg at 25 o C, respectively) makes it easy to use. Scheme S1. One-pot formation of (Ph 3 P)AuCl from HAuCl 4. Regarding the quantity of the sulfide used for the reduction, it was essential to minimize the amount of Pr 2 S in order to achieve the best yield of the complex. The use of 2.2 equivalents of sulfide gave almost quantitative yields. Separation of the complex by filtration showed lower yield (Table S1, entry 1) as compared to centrifugation (Table S1, entry 2). Further improvements involved tuning of reaction time and temperature to achieve better yields (Table S1, entries 3-5). Table S1. The yields and conditions for the synthesis of the (Ph 3 P)AuCl complex (R = Ph). Entry Conditions Precipitate separation Isolated yield, % 1 30 min.; 25 C filtration min; 25 C centrifugation min; 25 C centrifugation min; 40 С centrifugation min; 40 С centrifugation 99

3 S3 To compare the efficiency of the developed method with the reduction of HAuCl 4 by an excess of phosphine we conducted the series of experiments with various phosphorus ligands. It was shown in complete agreement with literature data that good to moderate yields can be achieved only with several phosphines (Table S2, entries, 1, 4-6). Even a slight variation in the phosphine ligand may lead to poor yields (Table S2). The introduction of the electron-withdrawing substituent into the aromatic ring of the phosphine ligand gave only trace amounts of products (Table S2, entries 2 and 3). Table S2. The yields in the synthesis of (R 3 P)AuCl complexes using the developed procedure of HAuCl 4 reduction by Pr 2 S and comparison with the literature data. Entry R 3 P (complex) Developed procedure (reduction with Pr 2 S) a Isolated yield, % Literature procedure (reduction with an excess of R 3 P) b 1 Ph 3 P (1) (4-F-C 6 H 4 ) 3 P (2) 99 8 c 3 (4-Cl-C 6 H 4 ) 3 P (3) 95 - d 4 (4-MeO-C 6 H 4 ) 3 P (4) c 5 (2-Me-C 6 H 4 ) 3 P (5) (2,6-(MeO) 2 -C 6 H 3 ) 3 P (6) c 7 (2-MeO-C 6 H 4 ) 3 P (7) 95 - d 8 CyPh 2 P (8) 95 6 c a Prepared by the method developed in the present study (see Experimental part for details); b Prepared according to the literature procedure of reduction of HAuCl 4 by an excess of corresponding phosphine (see below); c Poor product purity of ca. 65 to 90 % as determined by 31 P{ 1 H} NMR; d Formation of product was detected by 31 P{ 1 H} NMR, but it was impossible to isolate it in individual form from the reaction mixture using standard procedure.

4 S4 The developed procedure is very well suitable for the synthesis of complexes with stericaly demanding phosphine ligands, e.g. Buchwald-type (Table S3, entries 1-3). In all the cases the target complexes were isolated in 90-97% yield and excellent purity (preparation of these complexes by direct reduction with an excess of phosphine is impractical due to cost reasons). Table S3. The yields of (R 3 P)AuCl complexes with biphenylphosphine and phosphite ligands. Entry R 3 P Isolated yield, % (complex) Developed procedure Literature procedure a (9) (10) Cy 2 P O 3 t Bu O (11) P O t Bu 4 3 (12) a See article for discussion and references Synthesis of gold complexes by reduction of HAuCl 4 with an excess of phosphine. Literature procedure (Adopted from ref. 35 in the article) used for comparison (footnote b, Table S2): 100 mg (0.243 mmol) of HAuCl 4 4H 2 O was dissolved in 2 ml of ethanol resulting in the formation of clear golden-yellow solution. PPh 3 (127.4 mg, mmol) ligand was separately dissolved in 5 ml of hot ethanol. The solution of PPh 3 was added upon stirring to HAuCl 4 /ethanol

5 S5 which after 5 min yielded colorless reaction mixture and white precipitate. The stirring was continued for 30 min at rt. The white solid was filtered off, washed with 2x1 ml of ethanol, 2x1 ml of diethyl ether and dryed on the funnel. Yield: mg (90 %). Similar procedure was repeated for the other phoshines, although formation of precipitate at the end of reaction was not always the case. S2. Summary of the 31 P{ 1 H} NMR data for the prepared complexes. Table S4. Summary 31 P NMR data for the prepared complexes and free ligands δ( 31 P). Complex (R 3 P)AuCl, Free ligand (R 3 P), ppm ppm Ph 3 PAuCl (1) (4-F-C 6 H 4 ) 3 PAuCl (2) (4-Cl-C 6 H 4 ) 3 PAuCl (3) (4-MeO-C 6 H 4 ) 3 PAuCl (4) (2-Me-C 6 H 4 ) 3 PAuCl (5) (2,6-(MeO) 2 -C 6 H 3 )PAuCl (6) (2-MeO-C 6 H 4 ) 3 PAuCl (7) CyPh 2 PAuCl (8) (9) P( t Bu 2 )AuCl (10) t Bu (11) ClAuP O t Bu (12) S3. Characterization of the synthesized (R 3 P)AuCl complexes. Chloro(triphenylphosphine)gold (I) (1). 1 H NMR (CDCl 3, MHz, δ): (m, 15H). 13 C{ 1 H} NMR (CDCl 3, MHz, δ): (d, J = 62.4 Hz), (d, J = 11.6 Hz), , (d, J = 13.5 Hz). 31 P{ 1 H} NMR

6 S6 (CDCl 3, MHz, δ): HRMS (ESI): Calculated for C 18 H 15 PAu [M-Cl] = , found ( = 0.2 ppm). Chloro(tris(4-fluorophenyl)phosphine)gold (I) (2). 1 H NMR (CDCl 3, MHz, δ): (m, 6H), (m, 6H). 13 C{ 1 H} NMR (CDCl 3, MHz, δ): (m), (d, J = 65.4 Hz), (m), (d, J = Hz). 31 P{ 1 H} NMR (CDCl 3, MHz, δ): HRMS (ESI): Calculated for C 18 H 12 F 3 PAu [M-Cl] = , found ( = 0.4 ppm). Chloro(tris(4-chlorophenyl)phosphine)gold (I) (3). 1 H NMR (CDCl 3, MHz, δ): (m, 12H). 13 C{ 1 H} NMR (CDCl 3, MHz, δ): (d, J = Hz), (d, J = Hz), (d, J = 15 Hz), P{ 1 H} NMR (CDCl 3, MHz, δ): HRMS (ESI): Calculated for C 18 H 12 Cl 3 PAu [M-Cl] = , found ( = 2.7 ppm). Chloro(tris(4-methoxyphenyl)phosphine)gold (I) (4). 1 H NMR (CDCl 3, MHz, δ): 3.86 (s, 9H), (m, 6H), (m, 6H). 13 C{ 1 H} NMR (CDCl 3, MHz, δ): 55.41, (d, J = 13 Hz), (d, J = 68.5 Hz), (d, J = 15.3 Hz), P{ 1 H} NMR (CDCl 3, MHz, δ): HRMS (ESI): Calculated for C 21 H 21 O 3 ClPAu [M+Na] = , found ( = 0.8 ppm). Chloro(tris(2-methylphenyl)phosphine)gold (I) (5). 1 H NMR (CDCl 3, MHz, δ): 2.61 (s, 9H), 6.87 (m, 3H), 7.13 (t, J = 7.65 Hz, 3H), 7.29 (t, J = 6.42 Hz, 3H), 7.40 (t, J = 7.65 Hz, 3H). 13 C{ 1 H} NMR (CDCl 3, MHz, δ): (d, J = 11.2 Hz), (d, J = 61.3 Hz), (d, J = 10.4 Hz), , (d, J = 8.7 Hz), (d, J = 9.2 Hz), (d, J = 11.8 Hz). 31 P{ 1 H} NMR (CDCl 3, MHz, δ): HRMS (ESI): Calculated for C 21 H 21 ClPAu [M+Na] = , found ( = 1.4 ppm). Chloro(tris(2,6-dimethoxyphenyl)phosphine)gold (I) (6). 1 H NMR (CDCl 3, MHz, δ): 3.47 (s, 18H), 6.41 (m, 6H), 7.20 (t, J = 8.20 Hz, 3H). 13 C{ 1 H} NMR (CDCl 3, MHz, δ): 55.91, , , P{ 1 H} NMR (CDCl 3, MHz, δ): HRMS (ESI): Calculated for C 24 H 27 O 6 ClPAu [M+Na] = , found ( = 1.7 ppm). Chloro(tris(2-methoxyphenyl)phosphine)gold (I) (7). 1 H NMR (CDCl 3, MHz, δ): 3.62 (s, 9H), 6.87 (t, J = 7.36 Hz, 6H), 7.08 (m, 3H), 7.42 (t, J = 7.60 Hz, 3H). 13 C{ 1 H} NMR (CDCl 3, MHz, δ): 55.85, , (d, J = 66.3 Hz), (d, J = 11 Hz), , (d, J = 9 Hz), P{ 1 H} NMR (CDCl 3, MHz, δ): HRMS (ESI): Calculated for C 21 H 21 O 3 ClPAu [M+Na] = , found ( = 2.3 ppm). Chloro(cyclohexyl(diphenyl)phosphine)gold (I) (8).

7 S7 1 H NMR (CDCl 3, MHz, δ): 1.23 (m, 3H), 1.45 (m, 2H), 1.66 (s, 3H), 1.76 (m, 2H), 7.4 (m, 6H), 7.67 (m, 4H). 13 C{ 1 H} NMR (CDCl 3, MHz, δ): 25.73, (d, J = 14.8 Hz), (d, J = 38.1 Hz), (d, J = 57.5 Hz), (d, J = 11.1 Hz), , (d, J = 12.7 Hz). 31 P{ 1 H} NMR (CDCl 3, MHz, δ): HRMS (ESI): Calculated for C 18 H 21 PAu [M-Cl] = , found ( = 0.6 ppm). Chloro([1,1'-biphenyl]-2-yldicyclohexylphosphine)gold (I) (9). 1 H NMR (CDCl 3, MHz, δ): (m, 8H), (m, 2H), 1.60 (d, J = 12.5 Hz, 2H), 1.68 (d, J = 9.9 Hz, 2H), 1.77 (d, J = 9.9 Hz, 2H), 1.83 (d, J = 12.5 Hz, 2H), 1.98 (d, J = 12.2 Hz, 2H), 2.07 (m, 2H), 7.19 (d, J = 7.5 Hz, 2H), 7.32 (m, 1H), (m, 5H), 7.75 (t, J = 8.9 Hz, 1H). 13 C{ 1 H} NMR (CDCl 3, MHz, δ): 25.73, 26.52, 26.62, 26.70, 29.57, 31.32, (d, J = 33.5 Hz), (d, J=52.12 Hz), (d, J = 8.9 Hz), , , , , , , , , P{ 1 H} NMR (CDCl 3, MHz, δ): HRMS (ESI): Calculated for C 24 H 31 ClPAu [M+Na] = , found ( = 5.3 ppm). Chloro([1,1'-biphenyl]-2-yldi-tert-butylphosphine)gold (I) (10). 1 H NMR (CDCl 3, MHz, δ): 1.43 (d, J = 15.5 Hz, 18H), (d, J = 7.4 Hz, 2H), (t, J = 5.4 Hz, 1H), (t, J = 7.7 Hz, 2H), (m, 2H), (t, J = 7.7 Hz, 1H). 13 C{ 1 H} NMR (CDCl 3, MHz, δ): (d, J = 6.1 Hz), 37.9 (d, J = 26 Hz), (d, J = 5.62 Hz), , , , , (d, J = 6.5 Hz), P{ 1 H} NMR (CDCl 3, MHz, δ): HRMS (ESI): Calculated for C 20 H 27 PClAu [M+Na] = , found ( = 0.5 ppm). Chloro(dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine)gold (I) (11). 1 H NMR (CDCl 3, MHz, δ): (m, 8H), (m, 2H), (m, 8H), 1.97 (d, J = 11.5 Hz, 2H), (m, 2H), 3.71 (s, 6H), (d, J = 8.4 Hz, 2H), (m, 1H), (m, 4H). 13 C{ 1 H} NMR (CDCl 3, MHz, δ): 25.90, (d, J = 15.2 Hz), 29.41, 30.52, 36.40, 36.67, 55.50, , (d, J = 7.4 Hz), , , , (d, J = 7.7 Hz), P{ 1 H} NMR (CDCl 3, MHz, δ): HRMS (ESI): Calculated for C 26 H 35 O 2 ClPAu [M+Na] = , found ( = 1.5 ppm). Chloro(tris(2,4-di-tert-butylphenyl)phosphite)gold (I) (12). 1 H NMR (CDCl 3, MHz, δ): (s, 9H), (s, 9H), (d, J = 8.5 Hz, 1H), (m, 2H). 13 C{ 1 H} NMR (CDCl 3, MHz, δ): 30.69, 31.52, 34.80, 35.23, (d, J = 8.6 Hz), , , , , P{ 1 H} NMR (CDCl 3, MHz, δ): HRMS (ESI): Calculated for C 42 H 63 O 3 ClPAu [M+Na] = , found ( = 1.0 ppm).

8 S4. 31 P{ 1 H} NMR spectra of the prepared complexes. S8 31 P{ 1 H} NMR spectrum of chloro(triphenylphosphine)gold (I) (1). 31 P{ 1 H} NMR spectrum of chloro(tris(4-fluorophenyl)phosphine)gold (I) (2).

9 S9 31 P{ 1 H} NMR spectrum of chloro(tris(4-chlorophenyl)phosphine)gold (I) (3). 31 P{ 1 H} NMR spectrum of chloro(tris(4-methoxyphenyl)phosphine)gold (I) (4).

10 S10 31 P{ 1 H} NMR spectrum of chloro(tris(2-methylphenyl)phosphine)gold (I) (5). 31 P{ 1 H} NMR spectrum of chloro(tris(2,6-dimethoxyphenyl)phosphine)gold (I) (6).

11 S11 31 P{ 1 H} NMR spectrum of chloro(tris(2-methoxyphenyl)phosphine)gold (I) (7). 31 P{ 1 H} NMR spectrum of chloro(cyclohexyldiphenylphosphine)gold (I) (8).

12 S12 31 P{ 1 H} NMR spectrum of chloro([1,1'-biphenyl]-2-yldicyclohexylphosphine)gold (I) (9). 31 P{ 1 H} NMR spectrum of chloro([1,1'-biphenyl]-2-yldi-tert-butylphosphine)gold (I) (10).

13 S13 31 P{ 1 H} NMR spectrum of chloro(dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2- yl)phosphine)gold (I) (11). 31 P{ 1 H} NMR spectrum of chloro(tris(2,4-di-tert-butylphenyl)phosphite)gold (I) (12).

14 S14 S5. 13 C{ 1 H} NMR spectra of the prepared complexes. 13 C{ 1 H} NMR spectrum of chloro(triphenylphosphine)gold (I) (1). 13 C{ 1 H} NMR spectrum of chloro(tris(4-fluorophenyl)phosphine)gold (I) (2).

15 S15 13 C{ 1 H} NMR spectrum of chloro(tris(4-chlorophenyl)phosphine)gold (I) (3). 13 C{ 1 H} NMR spectrum of chloro(tris(4-methoxyphenyl)phosphine)gold (I) (4).

16 S16 13 C{ 1 H} NMR spectrum of chloro(tris(2-methylphenyl)phosphine)gold (I) (5). 13 C{ 1 H} NMR spectrum of chloro(tris(2,6-dimethoxyphenyl)phosphine)gold (I) (6).

17 S17 13 C{ 1 H} NMR spectrum of chloro(tris(2-methoxyphenyl)phosphine)gold (I) (7). 13 C{ 1 H} NMR spectrum of chloro(cyclohexyldiphenylphosphine)gold (I) (8).

18 S18 13 C{ 1 H} NMR spectrum of chloro([1,1'-biphenyl]-2-yldicyclohexylphosphine)gold (I) (9). 13 C{ 1 H} NMR spectrum of chloro([1,1'-biphenyl]-2-yldi-tert-butylphosphine)gold (I) (10).

19 S19 13 C{ 1 H} NMR spectrum of chloro(dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2- yl)phosphine)gold (I) (11). 13 C{ 1 H} NMR spectrum of chloro(tris(2,4-di-tert-butylphenyl)phosphite)gold (I) (12).

20 S20 S6. ESI-MS data for the prepared complexes. Table S5. Summary of ESI-MS data for the synthesized complexes. a Complex Molecular ion Calculated m/z Found m/z, ppm Ph 3 PAuCl (1) [M-Cl] (4-F-C 6 H 4 ) 3 PAuCl (2) [M-Cl] (4-Cl-C 6 H 4 ) 3 PAuCl (3) [M-Cl] (4-MeO-C 6 H 4 ) 3 PAuCl (4) [M+Na] (2-Me-C 6 H 4 ) 3 PAuCl (5) [M+Na] (2,6-(MeO) 2 -C 6 H 3 )PAuCl (6) [M+Na] (2-MeO-C 6 H 4 ) 3 PAuCl (7) [M+Na] CyPh 2 PAuCl (8) [M-Cl] P( t Bu 2 )AuCl (9) (10) [M+Na] [M+Na] [M+Na] t Bu (11) ClAuP O t Bu [M+Na] (12) a Corresponding experimental peaks and theoretically calculated peaks are show below.

21 S21 HRMS spectrum of chloro(triphenylphosphine)gold (I) (1). Experimental MS (top) and calculated MS (bottom). HRMS spectrum of chloro(tris(4-fluorophenyl)phosphine)gold (I) (2). Experimental MS (top) and calculated MS (bottom).

22 S22 HRMS spectrum of chloro(tris(4-chlorophenyl)phosphine)gold (I) (3). Experimental MS (top) and calculated MS (bottom). HRMS spectrum of chloro(tris(4-methoxyphenyl)phosphine)gold (I) (4). Experimental MS (top) and calculated MS (bottom).

23 S23 HRMS spectrum of chloro(tris(2-methylphenyl)phosphine)gold (I) (5). Experimental MS (top) and calculated MS (bottom). HRMS spectrum of chloro(tris(2,6-dimethoxyphenyl)phosphine)gold (I) (6). Experimental MS (top) and calculated MS (bottom).

24 S24 HRMS spectrum of chloro(tris(2-methoxyphenyl)phosphine)gold (I) (7). Experimental MS (top) and calculated MS (bottom). HRMS spectrum of chloro(cyclohexyldiphenylphosphine)gold (I) (8). Experimental MS (top) and calculated MS (bottom).

25 S25 HRMS spectrum of chloro([1,1'-biphenyl]-2-yldicyclohexylphosphine)gold (I) (9). Experimental MS (top) and calculated MS (bottom). HRMS spectrum of chloro([1,1'-biphenyl]-2-yldi-tert-butylphosphine)gold (I) (10). Experimental MS (top) and calculated MS (bottom).

26 S26 HRMS spectrum of chloro(dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine)gold (I) (11). Experimental MS (top) and calculated MS (bottom). HRMS spectrum of chloro(tris(2,4-di-tert-butylphenyl)phosphite)gold (I) (12). Experimental MS (top) and calculated MS (bottom).

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