Cyclams with ambidentate methylthiazolyl pendants for a stable, inert and selective Cu(II) coordination

Transcription

1 Supporting Information for: Cyclams with ambidentate methylthiazolyl pendants for a stable, inert and selective Cu(II) coordination Aurora Rodríguez-Rodríguez, Zakaria Halime, Luís M. P. Lima, Maryline Beyler, David Deniaud, Nicolas Le Poul, Rita Delgado,*, Carlos Platas-Iglesias*, Véronique Patinec, and Raphaël Tripier*, Université de Bretagne Occidentale, UMR-CNRS 6521, UFR des Sciences et Techniques, 6 avenue Victor le Gorgeu, C.S , BREST Cedex 3, France; Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Av. da República, Oeiras, Portugal; Université de Nantes, UMR CNRS 6230, UFR Sciences et Techniques, 2, rue de la Houssinière, BP 92208, Nantes, cedex 3, France; Grupo QUICOOR, Centro de Investigaciones Científicas Avanzadas (CICA) and Departamento de Química Fundamental, Facultade de Ciencias, Universidade da Coruña, Campus da Zapateira-Rúa da Fraga 10, A Coruña, Spain. (48 pages) 1

2 Summary Figure S1: 1 H (300 MHz), 31 C (75.5 MHz) and 31 P (121.5 MHz) NMR spectra of compound 3 (CDCl 3, 298 K).. p 4 Figure S2: HRMS spectra of compound 3 p 5 Figure S3: 1 H (300 MHz) and 31 C (75.5 MHz) NMR spectra of compound te1th (D 2O, 298 K). p 6 Figure S4: HRMS spectra of te1th.. p 7 Figure S5: 1 H (300 MHz) and 31 C (75.5 MHz) NMR spectra of compound 5 (D 2O, 298 K). p 8 Figure S6: HRMS spectra of compound 5 p 9 Figure S7: 1 H (300 MHz) and 31 C (75.5 MHz) NMR spectra of te2th (CDCl 3, 298 K) p 10 Figure S8: HRMS spectra of te2th. p 11 Figure S9: Views of the crystal structures of te1th 4HCl 2H 2O (left) and te2th 4H 2O (right). Hydrogen atoms linked to carbon atoms, anions and water molecules have been omitted for simplicity. The ORTEP plots are at the 30% probability level... p 12 Table S1: Crystal data and refinement details.. p 13 Figure S10: Speciation diagrams of the protonated species of te1th (left) and te2th (right) ligands in aqueous solution at [L] tot = 10-3 M.. p 14 Figure S11: Speciation diagrams of te1th (left) and te2th (right) ligands in presence of Cu 2+ in aqueous solution at [M 2+ ] tot = [L] tot = 10-3 M p 14 Figure S12: Speciation diagrams of te1th (left) and te2th (right) ligands in presence of Zn 2+ in aqueous solution at [M 2+ ] tot = [L] tot = 10-3 M.. p 14 Figure S13: 1 H (300 MHz) and 31 C (75.5 MHz) NMR spectra of compound [Znte1th](ClO 4) 2 (D 2O, 298 K).. p 15 Figure S14: 1 H (300 MHz) NMR spectra of compound te1h in the presence of various amounts of Zn(ClO 4) 2 (DMSO, K). p 15 Figure S15: COSY, HMQC and HMBC 2D NMR spectra ( 1 H: 500 MHz; 31 C: 125 MHz) of compound [Zntet1h](ClO 4) 2 (D 2O, K). p 16 Figure S16: 1 H (300 MHz) and 31 C (75.5 MHz) NMR spectra of compound [Znte2th](ClO 4) 2 (D 2O, K) p 17 Figure S17: 1 H (300 MHz) NMR spectra of compound [Znte2th](ClO 4) 2 at variable temperature (d 6-DMSO) p 18 Figure S18: 1 H (300 MHz) NMR spectra of compound [Znte2th](ClO 4) 2 at variable temperature (CD 3CN) p 18 Figure S19: COSY, HMQC and HMBC 2D NMR spectra ( 1 H: 500 MHz; 31 C: 125 MHz) of compound [Znte2th](ClO 4) 2 (CD 3CN, 295.2K). p 19 Figure S20. Optimized geometries of the trans-i, trans-iii and cis-v isomers of [Zn(te1th)] 2+ calculated in aqueous solution at the TPSSh/TZVP level. Bond distances of the metal coordination environments are given in Å.. p 20 Figure S21. Optimized geometries of the trans-iii and cis-v isomers of [Zn(te2th)] 2+ calculated in acetonitrile solution at the TPSSh/TZVP level. Bond distances of the metal coordination environments are given in Å.. p 21 Figure S22. Optimized geometries of the trans-i, trans-iii and cis-v isomers of [Cu(te1th)] 2+ calculated in aqueous solution at the TPSSh/TZVP level. Bond distances of the metal coordination environments are given in Å.. p 22 Figure S23. Optimized geometries of the trans-iii and cis-v isomers of [Cu(te2th)] 2+ calculated 2

3 in aqueous solution at the TPSSh/TZVP level. Bond distances of the metal coordination environments are given in Å.... p 23 Figure S24. Time course (% complexation versus time (s)) of Cu 2+ complexation by te1th (left) and te2th (right), C Ligand = 2.7 mm (1.0 equiv.), C Cu2+ = 51.6 mm (0.9 equiv.), I = 0.15 M, ph = 5.6 in acetate buffer at room temperature, followed by the increasing complex absorbance band respectively at nm and nm p 24 Figure S25. Time course of the copper(ii) complex of te1th in aqueous 5 M HCl solution at 50 C.. p 25 Figure S26. Time course of the copper(ii) complex of te2th in aqueous 5 M HCl solution at 30 C.. p 25 Figure S27. Time course of the copper(ii) complex of te2th in aqueous 5 M HCl solution at 50 C. p 25 Figure S28. Cyclic voltammogram of the [Cu(te2th)] 2+ complex obtained in neutral aqueous solution at ca. 1 mm using 0.1 M of NaClO 4 as electrolyte. p 25 Figure S29. Optimized geometry of the trans-i isomer of [Cu(te1th)] + calculated in acetonitrile solution at the TPSSh/TZVP level. Bond distances of the metal coordination environment are given in Å.. p 26 Table S2. Experimental (X-ray) bond lengths (Å) and angles ( ) of the metal coordination environment in [Cu(te1th)] 2+, [Cu(te2th)] 2+ and [Zn(te2th)] 2+. See figures for labeling.. p 27 Table S3. Relative Gibbs free energies [kj mol -1 ] of the different conformations of [Cu(te1th)] + obtained with DFT calculations in aqueous solution (TPSSh/TZVP).... p 28 Tables S4. Optimized Cartesian coordinates obtained with DFT calculations p

4 Figure S1: 1 H (300 MHz), 31 C (75.5 MHz) and 31 P (121.5 MHz) NMR spectra of compound 3 (CDCl 3, 298 K). 4

5 Figure S2: HRMS spectra of compound 3. 5

6 Figure S3: 1 H (300 MHz) and 31 C (75.5 MHz) NMR spectra of compound te1th (D 2 O, 298 K). 6

7 Figure S4: HRMS spectra of te1th. 7

8 Figure S5: 1 H (300 MHz) and 31 C (75.5 MHz) NMR spectra of compound 5 (D 2 O, 298 K). 8

9 Figure S6: HRMS spectra of compound 5. 9

10 Figure S7: 1 H (300 MHz) and 31 C (75.5 MHz) NMR spectra of te2th (CDCl 3, 298 K). 10

11 Figure S8: HRMS spectra of te2th. 11

12 Figure S9. Views of the crystal structures of te1th 4HCl 2H 2 O (left) and te2th 4H 2 O (right). Hydrogen atoms linked to carbon atoms, anions and water molecules have been omitted for simplicity. The ORTEP plots are at the 30% probability level. Crystals of the hydrochloride form of te1th (te1th 4HCl) were obtained from an acidified aqueous solution of the ligand. The four nitrogen atoms of the cyclam fragment are involved in hydrogen bonding interaction with the chloride anions. The te2th ligand crystallized in its neutral form in ethyl acetate, and presents a crystallographically imposed inversion center. The cyclam units in the two compounds adopt rectangular [3434] conformations. 1 The te2th ligand adopts an endodentate conformation that facilitates the coordination to metal ions, as observed for diprotonated cyclam in the form of different salts. 2 However, te1th 4HCl presents an exodentate conformation with the protonated nitrogen atoms at the corners of the rectangular [3434] unit. This conformation likely minimizes the electrostatic repulsion between the protonated nitrogen atoms and has been observed previously in different tetraprotonated cyclam salts. 3 (1) Dale, J. Acta Chem. Scand. 1973, 27, (2) a) Nave, C.; Truter, M. R. J. Chem. Soc., Dalton Trans. 1974, ; b) Ninon, M. O. M.; Fahim, F.; Lachkar, M.; Contelles, J. L. M.; Perles, J.; El Bali, B. Acta Cryst. 2013, E69, (3) a) Subramanian, S.; Zaworotko, M. J. Can. J. Chem. 1995, 73, ; b) Said, S.; Mhadhbi, N.; Hajlaoui, F.; Bataille, T.; Naïli, H. Acta Cryst. 2013, E69,

13 Table S1. Crystal data and refinement details. te1th 4HCl 3H 2 O te2th 4H 2 O formula C 14 H 37 N 5 Cl 4 O 3 S C 18 H 38 N 6 O 4 S 2 MW crystal system Monoclinic Monoclinic space group P 1 21/c 1 P 21/c T [K] 296(2) 298(2) a [Å] (3) (15) b [Å] (17) (18) c [Å] (4) (11) [deg] [deg] (4) (12) [deg] V [Å 3 ] (19) (3) F(000) Z 4 2 [Å] (MoK ) D calc [g cm -3 ] [mm -1 ] range [deg] R int reflns measd unique reflns reflns obsd GOF on F R1 a wr2 (all data) b Largest peak and hole /eå and and a R1 = F o - F c / F o. b wr2 = [w( F o 2 - F c 2 ) 2 ]/ [ w(f 4 o )] 1/2. 13

14 Figure S10: Speciation diagrams of the protonated species of te1th (left) and te2th (right) ligands in aqueous solution at [L] tot = 10-3 M. Figure S11: Speciation diagrams of te1th (left) and te2th (right) ligands in presence of Cu 2+ in aqueous solution at [M 2+ ] tot = [L] tot = 10-3 M. Figure S12: Speciation diagrams of te1th (left) and te2th (right) ligands in presence of Zn 2+ in aqueous solution at [M 2+ ] tot = [L] tot = 10-3 M. 14

15 Figure S13: 1 H (300 MHz) and 31 C (75.5 MHz) NMR spectra of compound [Znte1th](ClO 4 ) 2 (D 2 O, 298 K). Figure S14: 1 H (300 MHz) NMR spectra of compound te1th in the presence of various amounts of Zn(ClO 4 ) 2 (DMSO, K). 15

16 Figure S15: COSY, HMQC and HMBC 2D NMR spectra ( 1 H: 500 MHz; 31 C: 125 MHz) of compound [Znte1th](ClO 4 ) 2 (D 2 O, K). 16

17 Figure S16: 1 H (300 MHz) and 31 C (75.5 MHz) NMR spectra of compound [Znte2th](ClO 4 ) 2 (D 2 O, K). 17

18 Figure S17: 1 H (300 MHz) NMR spectra of compound [Znte2th](ClO 4 ) 2 at variable temperature (d 6 -DMSO). Figure S18: 1 H (300 MHz) NMR spectra of compound [Znte2th](ClO 4 ) 2 at variable temperature (CD 3 CN). 18

19 Figure S19: COSY, HMQC and HMBC 2D NMR spectra ( 1 H: 500 MHz; 31 C: 125 MHz) of compound [Znte2th](ClO 4 ) 2 (CD 3 CN, K). 19

20 Figure S20. Optimized geometries of the trans-i, trans-iii and cis-v isomers of [Zn(te1th)] 2+ calculated in aqueous solution at the TPSSh/TZVP level. Bond distances of the metal coordination environments are given in Å. 20

21 Figure S21. Optimized geometries of the trans-iii and cis-v isomers of [Zn(te2th)] 2+ calculated in acetonitrile solution at the TPSSh/TZVP level. Bond distances of the metal coordination environments are given in Å. 21

22 Figure S22. Optimized geometries of the trans-i, trans-iii and cis-v isomers of [Cu(te1th)] 2+ calculated in aqueous solution at the TPSSh/TZVP level. Bond distances of the metal coordination environments are given in Å. 22

23 Figure S23. Optimized geometries of the trans-iii and cis-v isomers of [Cu(te2th)] 2+ calculated in aqueous solution at the TPSSh/TZVP level. Bond distances of the metal coordination environments are given in Å. 23

24 Figure S24. Time course (%complexation versus time (s)) of Cu 2+ complexation by te1th (left) and te2th (right), C Ligand = 2.7 mm (1.0 equiv.), C Cu2+ = 51.6 mm (0.9 equiv.), I = 0.15 M, ph = 5.6 in acetate buffer at room temperature, followed by the increasing complex absorbance band respectively at 538 nm and 550 nm. Figure S25. Time course of the copper(ii) complex of te1th in aqueous 5 M HCl solution at 50 C: spectra obtained at 10 min intervals (left), and absorbance at 538 nm vs. time with fitting to the observed first order rate constant (right). 24

25 Figure S26. Time course of the copper(ii) complex of te2th in aqueous 5 M HCl solution at 30 C: spectra obtained at 3 min intervals (left), and absorbance at 550 nm vs. time with fitting to the observed first order rate constant (right). Figure S27. Time course of the copper(ii) complex of te2th in aqueous 5 M HCl solution at 50 C: spectra obtained at 1 min intervals (left), and absorbance at 550 nm vs. time with fitting to the observed first order rate constant (right). 1.0E E E+00 I /A -5.0E E E E E /mv vs. AgCl/Ag Figure S28. Cyclic voltammogram of the copper(ii) complex of te2th obtained in neutral aqueous solution at ca. 1 mm using 0.1 M of NaClO 4 as electrolyte. 25

26 Figure S29. Optimized geometry of the trans-i isomer of [Cu(te1th)] + calculated in acetonitrile solution at the TPSSh/TZVP level. Bond distances of the metal coordination environment are given in Å. 26

27 Table S2. Experimental (X-ray) bond lengths (Å) and angles ( ) of the metal coordination environment in [Cu(te1th)] 2+, [Cu(te2th)] 2+ and [Zn(te2th)] 2+. See figures for labeling. [Cu(te1th)].2ClO 4 [Cu(te2th)].2ClO 4 [Zn(te2th)].2ClO 4.H 2 O Cu(1)-N(1) Cu(1)-N(2) Cu(1)-N(3) Cu(1)-N(4) Cu(1)-N(5) 2.070(7) 1.971(8) 2.011(9) 2.008(8) 2.252(7) Cu(1)-N(1) Cu(1)-N(2) Cu(1)-N(3) (15) (15) (16) Zn(1)-N(1) Zn(1)-N(2) Zn(1)-N(3) Zn(1)-N(4) Zn(1)-N(5) Zn(1)-N(6) 2.202(3) 2.157(2) 2.203(2) 2.159(3) 2.220(3) 2.147(3) N(2)-Cu(1)-N(4) N(2)-Cu(1)-N(3) N(4)-Cu(1)-N(3) N(2)-Cu(1)-N(1) N(4)-Cu(1)-N(1) N(3)-Cu(1)-N(1) N(2)-Cu(1)-N(5) N(4)-Cu(1)-N(5) N(3)-Cu(1)-N(5) N(1)-Cu(1)-N(5) 165.6(3) 95.7(4) 86.1(4) 86.5(4) 90.9(4) 175.4(4) 98.0(3) 95.4(3) 103.7(3) 79.9(3) N(2)-Cu(1)-N(1) N(2)-Cu(1)-N(2) N(2)-Cu(1)-N(1) N(1)-Cu(1)-N(1) N(2)-Cu(1)-N(3) N(2)-Cu(1)-N(3) N(1)-Cu(1)-N(3) N(1)-Cu(1)-N(3) 86.54(6) (8) 93.46(6) (6) 90.09(6) (6) 79.39(6) N(6)-Zn(1)-N(2) N(6)- Zn(1)-N(4) N(2)- Zn(1)-N(4) N(6)- Zn(1)-N(1) N(2)- Zn(1)-N(1) N(4)- Zn(1)-N(1) N(6)- Zn(1)-N(3) N(2)- Zn(1)-N(3) N(4)- Zn(1)-N(3) N(1)- Zn(1)-N(3) N(6)- Zn(1)-N(5) N(2)- Zn(1)-N(5) N(4)- Zn(1)-N(5) N(1)- Zn(1)-N(5) N(3)- Zn(1)-N(5) (10) 90.69(10) 95.30(11) (10) 83.90(10) 90.79(10) 80.59(10) 90.58(10) 83.17(10) (10) 88.35(10) 87.47(10) (10) 79.45(10) (9) 27

28 Table S3. Relative Gibbs free energies [kj mol -1 ] of the different conformations of [Cu(te1th)] + obtained with DFT calculations in aqueous solution (TPSSh/TZVP). configuration Donor set [Cu(te1th)] + trans-i N trans-i N 4 S trans-iii N trans-iii N 4 S cis-v N cis-v N 4 S cis-v N Tables S4. Trans-I, [Cu(te1th)] 2+, TPSSh/TZVP, aqueous solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Number X Y Z

29 E(UTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Trans-III, [Cu(te1th)] 2+, TPSSh/TZVP, aqueous solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Number X Y Z

30 E(UTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Cis-V, [Cu(te1th)] 2+, TPSSh/TZVP, aqueous solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Number X Y Z

31 E(UTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Trans-III, [Cu(te2th)] 2+, TPSSh/TZVP, aqueous solution, 0 imaginary frequencies Atom Coordinates (Angstroms) X Y Z C H H C H H C H H C H H C H H C H H

32 C C H C H N N N S Cu H C H H C H H C H H C H H C H H C H H C C H C H N N N S H E(UTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Cis-V, [Cu(te2th)] 2+, TPSSh/TZVP, aqueous solution, 0 imaginary frequencies Atom Coordinates (Angstroms) X Y Z H H H C

33 H N H C C H H N C N H H C H H H C H C C H H H N C H H C H H H H C H H C S C C H H N Cu C H H C S C C H H N E(UTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies =

34 Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Trans-I, [Zn(te1th)] 2+, TPSSh/TZVP, aqueous solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Number X Y Z E(RTPSSh) = Hartree Zero-point correction =

35 Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Trans-III, [Zn(te1th)] 2+, TPSSh/TZVP, aqueous solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Number X Y Z

36 E(RTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Cis-V, [Zn(te1th)] 2+, TPSSh/TZVP, aqueous solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Type X Y Z

37 E(RTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Trans-III, [Zn(te2th)] 2+, TPSSh/TZVP, acetonitrile solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Number X Y Z

38 E(RTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Cis-V, [Zn(te2th)] 2+, TPSSh/TZVP, acetonitrile solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Number X Y Z

39 E(RTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Trans-I, N 5 -[Cu(te1th)] +, TPSSh/TZVP, acetonitrile solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Number X Y Z

40 E(RTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Trans-I, N 4 S-[Cu(te1th)] +, TPSSh/TZVP, acetonitrile solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) 40

41 Number Number X Y Z E(RTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies =

42 Trans-III, N 5 -[Cu(te1th)] +, TPSSh/TZVP, acetonitrile solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Number X Y Z E(RTPSSh) = Hartree Zero-point correction = Thermal correction to Energy =

43 Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Trans-III, N 4 S-[Cu(te1th)] +, TPSSh/TZVP, acetonitrile solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Number X Y Z

44 E(RTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Cis-V, N 5 -[Cu(te1th)] +, TPSSh/TZVP, acetonitrile solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Number X Y Z

45 E(RTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Cis-V, N 4 S-[Cu(te1th)] +, TPSSh/TZVP, acetonitrile solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Number X Y Z

46 E(RTPSSh) = Hartree Zero-point correction = Thermal correction to Energy = Thermal correction to Enthalpy = Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Energies = Sum of electronic and thermal Enthalpies = Sum of electronic and thermal Free Energies = Cis-V, N 4 -[Cu(te1th)] +, TPSSh/TZVP, acetonitrile solution, 0 imaginary frequencies Center Atomic Coordinates (Angstroms) Number Number X Y Z