Synthesis, Characterization and Simulations of Mixed-Metal Cluster Containing Pt-Ag 2 Cyclometalpropane. Supporting Information

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1 Synthesis, Characterization and Simulations of Mixed-Metal Cluster Containing Pt-Ag 2 Cyclometalpropane Xiaofei Zhang, a Bei Cao, a Edward J. Valente, b T. Keith Hollis,* a a Department of Chemistry and Biochemistry, The University of Mississippi, University, MS b University of Portland Diffraction Facility, Department of Chemistry and Biochemistry, University of Portland, Portland, OR Supporting Information 1. Excitation spectra of complexes 2, 3, 4 and 5 S2 2. Mass spectrometry of cluster 3 S3 3. Mass spectrometry, UV-Vis and Emission Spectra of complex 5 S4,5 4. X-ray crystallography details of 2, 3 and 4 S Details computational results S16-51 S1

2 1. Excitation spectra of complexes 2, 3, 4 and A.U Wavelength (nm) Figure S1. Excitation spectra of complexes 2, 3, 4 and 5 (detected at 450 nm) S2

3 2. Mass spectrometry of cluster 3 Figure S2. ESI-MS spectra of cluster 3. Insertions: experimental (line) and calculated (column) isotopic envelope of each peak. S3

4 3. Mass spectrometry, UV-Vis and Emission Spectra of complex AgOAc:Pt-Cl = Relative Intensity m/z AgOAc:Pt-Cl = Relative Intensity m/z Figure S3. Mass spectroscopy of complex 5. (1.0eq and 5.5eq AgOAc reactions) S4

5 UV-Vis absorption Absorbance (AU) eq 5.5eq Wavelength (nm) Figure S4. UV-Vis spectra of complexes 5 (1.0eq and 5.5eq AgOAc reactions) 100 Emission Relative Intensity eq 5.5 eq 5.2*10-3 M 5.5 eq 3.5*10-3 M 5.5 eq 2.1*10-3 M 5.5 eq 1.7*10-3 M 5.5 eq 8.9*10-4 M Wavelength (nm) Figure S5. Emission spectra of complexes 5 (1.0eq and 5.5eq AgOAc reactions and different concentrations. excited at 355 nm) S5

6 4. X-ray crystallography details of 2, 3 and (1,3-Bis(trimethylsilylmethyl-imidazol-2-ylidene)phenylene)(chloro) platinum (II), (2) Data collection The specimens were thin needles that nicely extinguished polarized light, but showed signs of twinning. The first specimen studied was twinned; a second is nicely ordered. The crystals were yellow, and a representative long needle specimen was cut (0.063 x x mm, and affixed to a fine glass fibre attached to a stout glass fibre mounted on a pin; the pin was placed on a goniometer head. The crystallographic properties and data were collected using MoKα radiation and the charge-coupled area detector (CCD) detector on an Oxford Diffraction Systems Gemini S diffractometer at 298(1)K (1). A preliminary set of cell constants was calculated from reflections observed on three sets of 5 frames which were oriented approximately in mutually orthogonal directions of reciprocal space. Data collection was carried out using MoKα radiation (graphite monochromator) with 8 runs consisting of 512 frames with a frame time of sec and a crystal-to-ccd distance of mm, and a strategy to achieve a resolution of 0.7Å. The runs were collected by omega scans of 1.0 width, and at detector position of , in 2θ. The intensity data were corrected for absorption with an analytical correction (4). Final cell constants were calculated from 7655 stronger reflections from the actual data collection after integration. See Table S1-1 through Table S1-6 for crystal and refinement information. Structure solution and refinement The crystal is monoclinic, C-centered, and the space group C2/c was determined from the cell geometry, reflections statistics, systematic absences, and successful solution and refinement. The structure was also solved in space group Cc, but the complex showed chemically unreasonable distortions, and it was clear that Cc was incorrect (Cc and C2/c cannot be told apart from systematic absences). The structure was solved by using direct methods in SHELXS-86(2b), and all non-h atoms were found in the E-map. Refinements were done using SHELXL-97(2a). All non-h atoms were refined and with anisotropic vibrational factors. H-atoms were observable in difference electron density maps, and placed in idealize positions; all were refined as riding atoms with relative isotropic displacement parameters of 120% of the U(eq) of the attached atom. One of the butyl side chains is disordered over two alternate conformations; the major conformer has occupancy 0.640(9). The final full-matrix least-squares refinement converged to R 1 = (2983 reflections, F2, I > 2σ(I)); R 1 = and wr 2 =.0383 for all 3663 data, 129 parameters, 0 restraints, goodness-of-fit (S) 0.999, and no extinction. S6

7 Structure description A half-molecule comprises the asymmetric unit, and complexes lie on the two-fold axis with the C-Pt-Cl exactly on the two-fold axis. The molecule has C 2 symmetry, and therefore can be limitingly close-packed in space group C 2 /c. Pt-C(1) is 2.024(3)Å, Pt-C(7) is 1.929(3)Å, while Pt-Cl is (9)Å. All other bond distances and angles are in normal ranges. There are no exceptional close contacts between molecules. 4.2 Pt 2 Ag 2 cluster, (3) Data collection The crystals were virgulate and extinguished nicely under crossed polarized light. One of the specimens, representative of the sample had dimensions x x mm 3. It was fixed to a fine glass fibre attached to a stout glass fibre mounted on a pin; the pin was placed on a goniometer head. The crystallographic properties and data were collected using MoKα radiation and the charge-coupled area detector (CCD) detector on an Oxford Diffraction Systems Gemini S diffractometer at 150(1) K (1). A preliminary set of cell constants was calculated from reflections observed on three sets of 5 frames which were oriented approximately in mutually orthogonal directions of reciprocal space. Data collection was carried out using MoKα radiation (graphite monochromator) with 6 runs consisting of 510 frames with a frame time of 60.0 sec and a crystal-to-ccd distance of mm, and a strategy to achieve a resolution of 0.7Å. The runs were collected by omega scans of 1.0 width, and at detector position of and in 2θ. The intensity data were corrected for absorption with an analytical correction (4). Final cell constants were calculated from stronger reflections from the actual data collection after integration. See Table S2-1 through Table S2-6 for crystal and refinement information. Structure solution and refinement The crystal is triclinic, space group P-1 (#2) as determined from the cell geometry, reflections statistics and successful solution and refinement. The structure was solved using by direct methods in SHELXS-86(2b), and all non-h atoms were found in the E-map. Refinements were done using SHELXL-97(2a). All non-h atoms were refined and with anisotropic vibrational factors. H-atoms were observable in difference electron density maps, and placed in idealize positions; all were refined as riding atoms with relative isotropic displacement parameters of 120% of the U(eq) of the attached atom. The trifluoroacetate salt was prepared with silver trifluoroacetate, and two equivalents of silver trifluoroacetate are incorporated into the dimerized structure. Solvent was located in the cell, which refined as a 0.77 pentane and an 0.23 hexane occupying a solvent location; the non-h atoms were modeled with isotropic vibrational S7

8 parameters; the hexane is fairly non-thermal, occupying the location tightly while the pentane is rather more thermal. The final full-matrix least-squares refinement converged to R 1 = (13754 reflections, F2, I > 2σ(I)); R 1 = and wr 2 = for all data, 794 parameters, 12 restraints (on C-C distances in the solvent), goodness-of-fit (S) 0.845, and no extinction. Structure description The structure is nominally the Pt complex as the trifluoroacetate, but dimerized on either side of two silver trifluoroacetates. PtAg 2 triangles are formed, with Pt-Ag distances of 2.93 and 3.14Å, with Ag-Ag distances of 2.94Å. The remaining Pt-Ag distance is 2.91Å. Other Information Data collection and structure solution were conducted at the University of Portland Diffraction Facility, 112A Swindells Hall, Department of Chemistry, University of Portland, Portland, OR, All calculations were performed using Pentium computers using the current SHELX suite of programs. Relevant References 1. CrysalisPro (2007), Version , Oxford Diffraction Ltd., Abingdon, Oxfordshire, OX14 4RX, United Kingdom. 2a. SHELX97 [Includes SHELXS97, SHELXL97, CIFTAB ] - Programs for Crystal Structure Analysis (Release 97-2). G. M. Sheldrick, Institüt für Anorganische Chemie der Universität, Tammanstrasse 4, D-3400 Göttingen, Germany, b. SHELXS86 - G. M. Sheldrick, In "Crystallographic Computing 3", Ed. G. M. Sheldrick, C. Kruger and R. Goddard, Oxford University Press. pp , SHELXS86 - Program for Crystal Structure solution. G. M. Sheldrick, Institüt für Anorganische Chemie der Universität, Tammanstrasse 4, D-3400 Göttingen, Germany, ORTEP3 for Windows - L. J. Farrugia, J. Appl. Crystallogr. 1997, 30, ABSORPTION CORRECTION (ANALYTICAL) - C. Katayama, Acta Crystallogr., Sect A 1986, 42, Wingx L.J. Farrugia, J. Appl. Cryst., 1999, 32, PLATON/PLUTON - (a) A. L. Spek, Acta Crystallogr., Sect A 1990, 46, C34. (b) PLATON, A Multipurpose Crystallographic Tool, Utrecht University, Utrecht, The Netherlands, A. L. Spek, S8

9 Relevant Equations used in this report: R int = Σ F o 2 -< F o 2 > / Σ F o 2 R 1 = Σ F o - F c / Σ F o wr2 = [Σ[w(F o 2-F c 2 ) 2 ] / Σ [w(f o 2 ) 2 ]] 1/2 where w = q / [σ 2 (F o 2) + (a*p) 2 + b*p + d + e*sin(θ)] GooF = S = [Σ[w(F o 2-F c 2 ) 2 ] / (n-p)] 1/2 S9

Figure S6. CCC-NHC-Pt-Cl 2 Figure S7. Unit cell of CCC-NHC-Pt-Cl 2 Table S1-1. Crystal data and structure refinement for 2. Empirical formula C 20 H 29 Cl N 4 Pt Si 2 Formula weight 612.

10 Figure S6. CCC-NHC-Pt-Cl 2 Figure S7. Unit cell of CCC-NHC-Pt-Cl 2 Table S1-1. Crystal data and structure refinement for 2. Empirical formula C 20 H 29 Cl N 4 Pt Si 2 Formula weight Temperature 298(2) K Wavelength Å Crystal system, space group Monoclinic, C 1 2/c 1 Unit cell dimensions a = (2) Å alpha = 90º b = (6) Å beta = (3) º c = (7) Å gamma = 90º Volume (14) Å 3 Z, Calculated density 4, Mg/m 3 Absorption coefficient mm -1 F(000) 1200 S10

11 Crystal size 0.69 x 0.11x 0.06 mm Theta range for data collection 3.40 to 30.60º Limiting indices -9 h 8, -27 k l 27 Reflections collected / unique / 3663 [R(int) = ] Completeness to theta = % Absorption correction Analytical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3663 / 0 / 129 Goodness-of-fit on F^ Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e.a -3 S11

12 Figure S8. Cluster Pt 2 Ag 2 3 Figure S9. Dimmer configuration of Cluster Pt 2 Ag 2 3. * One trifluoroacetate bridges neighboring dimers by H-bonding, with C-H O at 3.09 Å. S12

13 Table S2-1. Crystal data and structure refinement for 3. Empirical formula C 53 H 70 Ag 2 F 12 N 8 O 8 Pt Si 4 Formula weight Temperature 150(2) K Wavelength Å Crystal system, space group Triclinic, P -1 (#2) Unit cell dimensions a = (6) Å alpha = (4) b = (6) Å beta = (3) c = (6) Å gamma = (4) Volume (2) Å 3 Z, Calculated density 2, Mg/m 3 Absorption coefficient mm -1 F(000) 1688 Crystal size 0.50 x x 0.05 mm Theta range for data collection 3.52 to Limiting indices -21 h 21, -22 k 22, -23 l 21 Reflections collected / unique / [R(int) = ] Completeness to theta = % Absorption correction Analytical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 12 / 794 Goodness-of-fit on F^ Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e. Å -3 S13

14 Figure S10. CCC-NHC-Pt-O 2 CCF 3 4 Table S3-1. Crystal data and structure refinement for 4. Empirical formula C 22 H 29 F 3 N 4 O 2 Pt Si 2 Formula weight Temperature 293(2) K Wavelength Å Crystal system, space group Monoclinic P 2 1 /n Unit cell dimensions a = (12) Å alpha = 90º b = (4) Å beta = (7) º c = (4) Å gamma = 90º Volume (9) Å 3 Z, Calculated density 4, Mg/m 3 Absorption coefficient mm -1 S14

15 F(000) 1352 Crystal size 0.36 x 0.20x 0.15 mm Theta range for data collection 3.17 to 27.48º Limiting indices -8 h 8, -25 k l 26 Reflections collected / unique / 6155 [R(int) = ] Absorption correction Analytical Max. and min. transmission and Data / restraints / parameters 6155 / 76 / 381 Goodness-of-fit Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e.a -3 S15

16 5. Detailed computational result. kcal/mol E M PBEPBE twisted head to head head to tail 2.6 TPSSTPSS 2.5 B3LYP Figure S11. Relative stabilization energy of hypothetical head to head and head to tail configurations of Pt 2 Ag 2 cluster 3. Cartesian geometries (in Ångstroms), Stationary point TDDFT energies (in Hartrees) S16

17 Figure S12. TPSSTPSS optimized configuration of Complex Pt-O 2 CCF 3 4. Pt-O 2 CCF 3 output Pt Si Si O O C C F F F N N N N C C H C H C C C H C H C H H C H H H C H H H S17

18 C H H H C H C C C H C H C H H C H H H C H H H C H H H S18

19 Figure S13. PBEPBE optimized configuration of Complex Pt-O 2 CCF 3 4. Pt-O 2 CCF 3 output Pt Si Si O O C C F F F N N N N C C H C H S19

20 C C C H C H C H H C H H H C H H H C H H H C H C C C H C H C H H C H H H C H H H C S20

21 H H H Figure S14. B3LYP optimized configuration of Complex Pt-O 2 CCF 3 4. Pt-O 2 CCF 3 output Pt Si Si O O C C F F F N N N N S21

22 C C H C H C C C H C H C H H C H H H C H H H C H H H C H C C C H C H C H H C H H H S22

C 4.330933-3.50844-0.20555 H 4.877247-4.00953-1.01674 H 3.351764-3.99431-0.11917 H 4.884471-3.68932 0.726052 C 5.845384-0.88562-0.81425 H 6.345346-1.32016-1.6911 H 6.503047-1.05044 0.050987 H 5.

23 C H H H C H H H Figure S15. M06 optimized configuration of Complex Pt-O 2 CCF 3 4. Pt-O 2 CCF 3 output Pt Si Si O O C C F F S23

24 F N N N N C C H C H C C C H C H C H H C H H H C H H H C H H H C H C C C H C H C H S24

H 3.869661-0.57469 2.023791 C 3.231827-0.84944-1.96085 H 2.249707-1.33304-1.87253 H 3.755061-1.27533-2.82915 H 3.05812 0.217187-2.16649 C 4.665336-2.86739-0.05432 H 5.29965-3.28529-0.84882 H 3.

25 H C H H H C H H H C H H H Figure S16. TPSSTPSS optimized configuration of Cluster Pt 2 Ag 2 3. Pt 2 Ag 2 twisted output SCF Done: E(RTPSS-TPSS) = S25

26 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C S26

27 C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S27

28 H H H H H H H H H H H H H H H H H H H H H H H H N N N N N N N N O O O O O O O O F S28

29 F F F F F F F F F F F Si Si Si Si Ag Ag Pt Pt S29

Figure S17. PBEPBE optimized configuration of Cluster Pt 2 Ag 2 3. Pt 2 Ag 2 twisted output C 7.919311 1.487882-0.84525 C 5.558897-1.18068-2.01404 C 5.214319-2.49286-1.80063 C 4.839071 1.068584-1.

30 Figure S17. PBEPBE optimized configuration of Cluster Pt 2 Ag 2 3. Pt 2 Ag 2 twisted output C C C C C C C C C C C C C C S30

31 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C H H H H H H H S31

32 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S32

33 H H H H H H H H H H N N N N N N N N O O O O O O O O F F F F F F F F F F F F Si Si Si S33

Si -6.45257-1.6512 1.202106 Ag 1.31069-0.43362-1.93228 Ag -0.44271-0.72067 0.335224 Pt 2.536769-1.07021 1.058444 Pt -2.82122 0.365575-1.09343 Figure S18.

34 Si Ag Ag Pt Pt Figure S18. B3LYP optimized configuration of Cluster Pt 2 Ag 2 3. Pt 2 Ag 2 twisted output C C C C C C C S34

35 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C S35

36 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S36

37 H H H H H H H H H H H H H H H H H N N N N N N N N O O O O O O O O F F F F F F F F S37

F 1.426415 3.530448 2.685028 F -3.18122 2.165143 3.644157 F -4.84274 0.763937 3.501333 F -3.00766 0.178087 4.499066 Si 6.447443 1.651249-0.00801 Si 1.673001 0.188977 5.505042 Si -3.46674 5.117442 0.

38 F F F F Si Si Si Si Ag Ag Pt Pt Figure S19. M06 optimized configuration of Cluster Pt 2 Ag 2 3. Pt 2 Ag 2 twisted output C S38

39 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C S39

40 C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S40

41 H H H H H H H H H H H H H H H H H H H H H H H N N N N N N N N O O O O O O O O F F S41

F -2.5451670-4.1352890-2.4118290 F -1.3762220 5.4093480-1.8736060 F 0.5525330 4.9974040-2.7300040 F 0.3953530 5.6182650-0.6726770 F -1.1456670-4.1527800-0.0165490 F -2.7849940-3.8563600 1.

42 F F F F F F F F F F Si Si Si Si Ag Ag Pt Pt S42

43 Figure S20. TPSSTPSS optimized modeled hypothetical head to head configuration of Cluster Pt 2 Ag 2 3. Pt 2 Ag 2 head to head output SCF Done: E(RTPSS-TPSS) = C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C S43

44 C C C C C C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S44

45 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H N N N N N N N N O O O O S45

46 O O F F F F F F F F F Si Si Si Si Ag Pt Pt C O O C F F F Ag S46

47 Figure S21. TPSSTPSS optimized modeled hypothetical head to tail configuration of Cluster Pt 2 Ag 2 3. Pt 2 Ag 2 head to tail output SCF Done: E(RTPSS-TPSS) = C C C C C C C C C C C C S47

48 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C H H H H H H H S48

49 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S49

50 H H H H H H H H H H N N N N N N N N O O O O O O F F F F F F F F F Si Si Si Si Ag Pt Pt C S50

51 O O C F F F Ag Reference for Gaussian 09 Program: (1) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; J. A. Montgomery, J.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revisions, A.02, Gaussian, Inc. Wallingford, CT, S51

Group 13 BN dehydrocoupling reagents, similar to transition metal catalysts but with unique reactivity. Part A: NMR Studies

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